201202376 六、發明說明： 【發明所屬之技術領域】 本發明係關於壓感黏合劑組成物、用於光學元件的保 護膜、偏光器和液晶顯示裝置。 【先前技術】 液晶顯示裝置包括各式各樣的光學元件，如偏光器、 阻滞板、光學補償膜、反射片或亮光增進膜。欲在製造液 晶顯示裝置或製造之後的運送和分配的期間內保護此光學 元件，保護膜可附於其上。 在用於光學元件的保護膜中，極重要的是根據剝除速 率控制剝除力。例如，保護膜須於低速率具有適當剝除力 以扮演其角色。若於低速率的剝除力過低，則易於打造光 學元件時發生浮起的情況，因此而易受到外界的污染。 製造液晶顯示裝置的期間內，光學元件的保護膜於某 些時間移除，就產製觀點，其於高速率自光學元件移除。 因此，若壓感黏合劑於高速率的剝除力過高，則液晶面板 受損，及因爲靜電力過大而造成面板中的驅動裝置等受損 〇 據此，用於光學元件之保護膜中的壓感黏合劑必須同 時兼具於低速率的高剝除力及於高速率的低剝除力。 但是，壓感黏合劑於高速率和低速率的剝除力將取決 於交聯程度等而同時提高或降低。因此，難題在於使得黏 著劑於低速率具有高剝除力及於高速率具有低剝除力。 -5- 201202376 例如’專利案參考資料丨至4揭示各式各樣的壓感黏合 劑’但該壓感黏合劑的問題在於於低速率和高速率的剝除 力之平衡欠佳’及對於被黏合物的潤濕性或黏合性欠佳等 [以前技術參考資料] (專利案參考資料1 ) 163468 (專利案參考資料2 ) 256111 (專利案參考資料3 ) 323239 (專利案參考資料4 ) 023143 曰本專利申請公告 H05-曰本專利申請公告 H11-日本專利申請公告 200 1 -日本專利申請公告 2005- 【發明內容】 [技術問題] 本發明欲提出壓感黏合劑組成物，用於光學元件、偏 光器和液晶顯示裝置之保護膜。 [技術手段] 本發明係關於一種壓感黏合劑組成物，其包含重量平 均分子量爲1，1〇〇,〇〇〇或更低的丙烯酸系樹脂，其中在硬 化之後，該組成物包含具有處於交聯態的該丙烯酸系樹脂 -6- 201202376 之互相貫穿的聚合物網絡結構（下文中通常稱爲“IPN”） ，且在包括該結構的狀態下，於剝除角度1 和剝除速率 0.3米/分鐘測定時，對TAC (三乙醯基纖維素）片的剝 除力爲8至40克力/英吋，及於剝除角度18 0°和剝除速率 3 0米/分鐘測定時，對TAC片的剝除力爲80至300克力/ 英吋。 下文更詳細地解釋該壓感黏合劑組成物。 【實施方式】 本壓感黏合劑組成物包含重量平均分子量爲 1，1 00,0 00或更低的丙烯酸系樹脂，其中在硬化之後，該 組成物包含具有處於交聯態的該丙烯酸系樹脂之IPN結構 ，及該交聯結構以外的交聯結構。 “令壓感黏合劑組成物硬化”是指壓感黏合劑組成物照 光或維持於某些溫度以藉物理作用或化學作用發展黏合性 質的狀態。此處之硬化的壓感黏合劑組成物可以選擇性地 具有與壓感黏合劑或壓感黏合層相同的意義。 此外，“照光”是指以電磁波照射，其中該電磁波的例 子包括微波、紅外光（IR)、紫外光（UV) 、X-射線和 γ-射線，或粒子束（如α-粒子束）、質子束、中子束和電 子束。 “ΙΡΝ結構”是指在硬化之後，至少兩個交聯的結構同 時存在於壓感黏合劑中。一個特點中，該至少兩個交聯結 構可處於彼此交纏的狀態。即，本發明之壓感黏合劑組成 201202376 物包含至少一個該丙烯酸系樹脂交聯並含括於其中的交聯 結構及含括於該丙烯酸系樹脂中之交聯結構以外的另一交 聯結構。此處，互相貫穿的聚合物網絡結構中之丙烯酸系 樹脂可以處於藉多官能***聯劑交聯的狀態。以多官能性 交聯劑交聯之丙烯酸系樹脂的交聯結構可藉由使用可交聯 的丙烯酸系樹脂作爲該壓感黏合劑組成物中所含括之具有 某些分子量的丙烯酸系樹脂，並令此可交聯的丙烯酸系樹 脂與多官能***聯劑在使壓感黏合劑組成物硬化的方法中 交聯而含括。“可交聯的丙烯酸系樹脂”是指可與下文所述 之多官能***聯劑反應之官能基存在於其側鏈或末端的丙 烯酸系樹脂》 考慮包含IPN結構的壓感黏合劑的剝除力，使用重量 平均分子量（Mw)爲1，1 00,000或更低的丙烯酸系樹脂作 爲該丙烯酸系樹脂。於低和高速率之適當的剝除力特性可 藉由使用重量平均分子量爲1,1 00,000或更低的樹脂（其 在組成物硬化之後，以經多官能***聯劑交聯的狀態含括 於IPN中）而體現。此處的重量平均分子量是指藉GPC ( 凝膠穿透層析法）測定，以聚苯乙烯爲標準品，轉換而得 的値，特定言之，是指藉下文所述之測定方法1中指定的 方法測得的値。同樣地，除非特別聲明，否則“分子量”是 指“重量平均分子量”。 該丙烯酸系樹脂的分子量較佳爲1 0,000,000或更低， 更佳爲800,000或更低，且又更佳爲600,000或更低。未特 別限制該丙烯酸系樹脂的分子量下限，且例如，考慮壓感 -8- 201202376 黏合劑的黏合力或耐久性，可控制在 較佳約300,000或更高的範圍內。 一個特點中，該丙烯酸系樹脂包1 單體：和可交聯單體作爲聚合單元。 例如，可以使用（甲基）丙烯酸夫 丙烯酸酯單體，考慮黏合力、玻璃化轉 等，可以使用烷基具1至14個碳原子（¾ )的（甲基）丙烯酸烷酯。此（甲基） 可包括（甲基）丙烯酸甲酯、（甲基） 基）丙烯酸正丙酯、（甲基）丙烯酸異 烯酸正丁酯、（甲基）丙烯酸三級丁醋 二級丁酯、（甲基）丙烯酸戊酯、（甲 己酯、（甲基）丙烯酸2-乙基丁酯、（ 酯、（甲基）丙烯酸異辛酯、（甲基） 甲基）丙烯酸月桂酯和（甲基）丙烯酸 的一或至少二者可含於樹脂中作爲聚合 此外，該可交聯單體是指，例如， 烯酸酯單體共聚並在共聚反應之後提供 之單體。 該可交聯官能基可包括，例如，經 基、異氰酸酯基或含氮官能基等，其中 羧基。此領域中，已經知道可使用之各 體，考慮所欲之可交聯的官能基，其中 單體。這些單體的例子包括含有羥基的 弓1 50,000或更高， (甲基）丙烯酸酯 酯作爲該（甲基） 變溫度、或剝除力 交佳1至12個碳原子 丙烯酸烷酯的例子 丙烯酸乙酯、（甲 丙酯、（甲基）丙 、（甲基）丙烯酸 基）丙烯酸2-乙基 甲基）丙烯酸正辛 丙烯酸異壬酯、（ 十四烷酯等，其中 單元。 可與該（甲基）丙 樹脂可交聯官能基 基、羧基、環氧丙 一般可使用羥基或 式各樣的可交聯單 可使用所有的這些 單體，如（甲基） -9- 201202376 丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙 烯酸4-羥丁酯、（甲基）丙烯酸6-羥己酯、（甲基）丙烯 酸8-羥辛酯、（甲基）丙烯酸2-羥基乙二醇酯或（甲基） 丙烯酸2 _羥基丙二醇酯；含羧基的單體，如（甲基）丙烯 酸、2-(甲基）丙烯醯氧基乙酸、3-(甲基）丙烯醯氧基 丙酸、4-(甲基）丙烯醯氧基丁酸、丙烯酸二聚合物、衣 康酸、順-丁烯二酸和順-丁烯二酸酐；或含氮單體，如（ 甲基）丙烯醯胺、N-乙烯基吡咯烷酮或N-乙烯基己內醯胺 等，其中的一或至少二者可含括於該丙烯酸系樹脂中作爲 聚合單元，但不限於此。 該丙烯酸系樹脂可包含8 0至99.8重量份該（甲基）丙 烯酸酯單體和0.01至10重量份可交聯單體作爲聚合單元， 藉此適當地維持物理性質，如黏合力、剝除力和耐久性。 此處’除非特別聲明，否則“重量份”是指重量比。 必要時，該丙烯酸系樹脂另包含以下列化學式1表示 的單體作爲聚合反應的單元。 [化學式1]201202376 VI. Description of the Invention: [Technical Field] The present invention relates to a pressure-sensitive adhesive composition, a protective film for an optical element, a polarizer, and a liquid crystal display device. [Prior Art] A liquid crystal display device includes various optical elements such as a polarizer, a retardation plate, an optical compensation film, a reflection sheet, or a light enhancement film. To protect the optical element during the manufacture of the liquid crystal display device or during transport and dispensing after manufacture, a protective film can be attached thereto. In the protective film for optical elements, it is extremely important to control the stripping force in accordance with the stripping rate. For example, the protective film must have a suitable stripping force at a low rate to play its role. If the stripping force at a low rate is too low, it is easy to create an optical component when it floats, and thus is susceptible to external pollution. During the manufacture of the liquid crystal display device, the protective film of the optical element is removed at a certain time, and the viewpoint is produced, which is removed from the optical element at a high rate. Therefore, if the pressure-sensitive adhesive is excessively high at a high rate, the liquid crystal panel is damaged, and the driving device or the like in the panel is damaged due to an excessive electrostatic force, thereby being used in the protective film of the optical element. The pressure-sensitive adhesive must have both a low rate of high stripping force and a high rate of low stripping force. However, the peeling force of the pressure-sensitive adhesive at a high rate and a low rate will be increased or decreased depending on the degree of crosslinking or the like. Therefore, the difficulty is to make the adhesive have a high peeling force at a low rate and a low peeling force at a high rate. -5- 201202376 For example, 'Patent References 丨 to 4 disclose a wide variety of pressure sensitive adhesives' but the problem with this pressure sensitive adhesive is that the balance of low and high rate stripping forces is poor' and Poor wettability or adhesiveness of the adhesive etc. [Previous technical reference] (Patent Reference 1) 163468 (Patent Reference 2) 256111 (Patent Reference 3) 323239 (Patent Reference 4) 023143 曰 专利 专利 H 05 05 05 05 05 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 A protective film for components, polarizers, and liquid crystal display devices. [Technical means] The present invention relates to a pressure-sensitive adhesive composition comprising an acrylic resin having a weight average molecular weight of 1,1 Torr, lanthanum or less, wherein after hardening, the composition contains The cross-linked polymer network structure of the acrylic resin-6-201202376 (hereinafter generally referred to as "IPN"), and in the state including the structure, at the stripping angle 1 and the stripping rate of 0.3 When measured in meters per minute, the stripping force for TAC (triethylenesulfonyl cellulose) sheet is 8 to 40 gram force/inch, and at the peeling angle of 18 0° and the stripping rate of 30 m/min. The stripping force for TAC sheets is 80 to 300 gram force per inch. The pressure sensitive adhesive composition is explained in more detail below. [Embodiment] The pressure-sensitive adhesive composition contains an acrylic resin having a weight average molecular weight of 1,100,000 or less, wherein after curing, the composition contains the acrylic resin having a crosslinked state. The IPN structure and the crosslinked structure other than the crosslinked structure. By "hardening the pressure-sensitive adhesive composition" is meant a state in which the pressure-sensitive adhesive composition is illuminated or maintained at a certain temperature to develop an adhesive property by physical or chemical action. The hardened pressure-sensitive adhesive composition herein may optionally have the same meaning as the pressure-sensitive adhesive or the pressure-sensitive adhesive layer. Further, "illumination" means irradiation with electromagnetic waves, and examples of the electromagnetic waves include microwaves, infrared light (IR), ultraviolet light (UV), X-rays, and γ-rays, or particle beams (such as α-particle beams), Proton beam, neutron beam, and electron beam. "ΙΡΝ structure" means that at least two crosslinked structures are present in the pressure sensitive adhesive simultaneously after hardening. In one feature, the at least two crosslinked structures may be in a state of being intertwined with each other. That is, the pressure-sensitive adhesive composition 201202376 of the present invention contains at least one crosslinked structure in which the acrylic resin is crosslinked and included, and another crosslinked structure other than the crosslinked structure included in the acrylic resin. . Here, the acrylic resin in the interpenetrating polymer network structure may be in a state of being crosslinked by a polyfunctional crosslinking agent. The crosslinked structure of the acrylic resin crosslinked by the polyfunctional crosslinking agent can be obtained by using a crosslinkable acrylic resin as an acrylic resin having a certain molecular weight included in the composition of the pressure sensitive adhesive, and The crosslinkable acrylic resin and the polyfunctional crosslinking agent are crosslinked in a method of curing the pressure-sensitive adhesive composition. "Crosslinkable acrylic resin" means an acrylic resin in which a functional group reactive with a polyfunctional crosslinking agent described below is present at a side chain or a terminal thereof." Desorption of a pressure-sensitive adhesive containing an IPN structure is considered. As the acrylic resin, an acrylic resin having a weight average molecular weight (Mw) of 1,100,000 or less was used. Suitable stripping force characteristics at low and high rates can be achieved by using a resin having a weight average molecular weight of 1,100,000 or less (which is included in the state of being crosslinked by a polyfunctional crosslinking agent after the composition is hardened). Reflected in the IPN). The weight average molecular weight herein refers to a ruthenium converted by GPC (gel permeation chromatography) and polystyrene as a standard. In particular, it refers to the measurement method 1 described below. The measured method is measured by 値. Similarly, "molecular weight" means "weight average molecular weight" unless otherwise stated. The acrylic resin preferably has a molecular weight of 10,000,000 or less, more preferably 800,000 or less, and still more preferably 600,000 or less. The lower limit of the molecular weight of the acrylic resin is not particularly limited, and for example, in view of the adhesive strength or durability of the pressure sensitive adhesive -8 to 201202376, it can be controlled to be preferably in the range of about 300,000 or more. In one feature, the acrylic resin package 1 monomer: and a crosslinkable monomer are used as a polymerization unit. For example, a (meth)acrylic acrylate monomer can be used, and an alkyl (meth) acrylate having 1 to 14 carbon atoms (3⁄4 ) in an alkyl group can be used in view of adhesion, vitrification, and the like. This (methyl) may include methyl (meth)acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and tertiary butyl acrylate (meth) acrylate. Ester, amyl (meth)acrylate, (methylhexyl ester, 2-ethylbutyl (meth)acrylate, (ester, isooctyl (meth)acrylate, (methyl)methyl) lauryl acrylate and One or at least two of (meth)acrylic acid may be contained in the resin as a polymerization. Further, the crosslinkable monomer means, for example, a monomer copolymerized with an enoate monomer and supplied after the copolymerization reaction. The co-functional group may include, for example, a trans-group, an isocyanate group or a nitrogen-containing functional group, etc., wherein a carboxyl group. In the art, it is known that each body can be used, considering the desired crosslinkable functional group, wherein the monomer. Examples of such monomers include those having a hydroxyl group-containing bow of 150,000 or more, a (meth) acrylate ester as the (meth) variability temperature, or a stripping power of preferably 1 to 12 carbon atoms of an alkyl acrylate. Ethyl ester, (methyl propyl ester, (methyl) propyl, ( (meth)acrylic acid) 2-ethylmethyl)acrylic acid n-octyl isopropyl isophthalate, (tetradecyl ester, etc., wherein the unit can be crosslinked with the (meth) propylene resin functional group, carboxyl group, ring Oxygen can generally use all of these monomers using hydroxyl groups or a variety of crosslinkable monomers, such as (methyl)-9-201202376 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate or (methyl) 2-Hydroxypropylene glycol acrylate; carboxyl group-containing monomer such as (meth)acrylic acid, 2-(meth)acryloxyacetic acid, 3-(meth)acryloxypropionic acid, 4-(methyl Acryloxybutyric acid, acrylic acid dipolymer, itaconic acid, maleic acid, and maleic anhydride; or nitrogen-containing monomer such as (meth)acrylamide, N-vinyl Pyrrolidone or N-vinyl caprolactam, etc., one or at least two of which may be included in the acrylic resin as a polymerization unit, but The acrylic resin may contain 80 to 99.8 parts by weight of the (meth) acrylate monomer and 0.01 to 10 parts by weight of a crosslinkable monomer as a polymerization unit, thereby appropriately maintaining physical properties such as bonding. Force, peeling power and durability. Here, 'parts by weight, unless otherwise stated, means a weight ratio. If necessary, the acrylic resin further contains a monomer represented by the following Chemical Formula 1 as a unit of polymerization reaction. Chemical formula 1]
R/ R4 其中1^至R3各者獨立地代表氫或烷基；r4代表氰基、 未經取代或經烷基、乙醯氧基或COR5 (其中R5代表胺基 或環氧丙氧基，其未經取代或經烷基或烷氧基烷基取代） -10- 201202376 取代的苯基。 該化學式1的單體可用以進一步控制壓感黏合劑的物 理性質或提供其他官能性。 該化學式1中之1^至115的定義中，烷基或烷氧基是指 具1至8個碳原子的烷基或烷氧基，且較佳地，可爲甲基、 乙基、甲氧基' 乙氧基、丙氧基或丁氧基。 相對於前述丙烯酸系樹脂中之（甲基）丙烯酸酯單體 或可交聯單體之重量比，該化學式1的單體的含量可爲， 例如，20重量份或更低。 前述丙烯酸系樹脂可藉此領域中已知的一般聚合法製 得。例如’其可根據所欲重量比，藉適當地調合（甲基） 丙烯酸酯單體、可交聯單體和/或化學式1的單體等，以 製造用於一般聚合法（如溶液聚合法、光聚合法、整體聚 合法、懸浮聚合法或乳化聚合法）的單體混合物。此程序 中’必要時’可以一倂使用適當的聚合反應引發劑或鏈轉 移劑等。 該壓感黏合劑組成物可另包含能夠與該丙烯酸系樹脂 反應以在硬化程序期間內體現交聯結構的多官能***聯劑 〇 考慮含括於該丙烯酸系樹脂中之可交聯官能基的同時 ’例如’可以使用適當種類的已知交聯劑（如異氰酸酯交 聯劑、環氧基交聯劑、吖啶交聯劑和金屬鉗合劑交聯劑） 作爲多官能***聯劑。該異氰酸酯交聯劑的例子可包括具 有至少兩個異氰酸酯基的化合物，如二異氰酸甲酸苯酯、R/ R4 wherein each of 1^ to R3 independently represents hydrogen or alkyl; r4 represents cyano, unsubstituted or alkyl, ethoxylated or COR5 (wherein R5 represents an amine or a epoxypropoxy group, a phenyl group which is unsubstituted or substituted by an alkyl or alkoxyalkyl group) -10- 201202376. The monomer of Formula 1 can be used to further control the physical properties of the pressure sensitive adhesive or to provide other functionalities. In the definition of 1^ to 115 in the chemical formula 1, the alkyl group or the alkoxy group means an alkyl group or alkoxy group having 1 to 8 carbon atoms, and preferably, may be a methyl group, an ethyl group, or a group Oxy' ethoxy, propoxy or butoxy. The content of the monomer of the Chemical Formula 1 may be, for example, 20 parts by weight or less based on the weight ratio of the (meth) acrylate monomer or the crosslinkable monomer in the acrylic resin. The aforementioned acrylic resin can be produced by a general polymerization method known in the art. For example, it can be used for general polymerization (such as solution polymerization) by appropriately blending a (meth) acrylate monomer, a crosslinkable monomer, and/or a monomer of Chemical Formula 1 according to a desired weight ratio. A monomer mixture of a photopolymerization method, a monolithic polymerization method, a suspension polymerization method or an emulsion polymerization method. In the procedure, if necessary, a suitable polymerization initiator or chain transfer agent or the like can be used. The pressure-sensitive adhesive composition may further comprise a polyfunctional crosslinking agent capable of reacting with the acrylic resin to exhibit a crosslinked structure during the curing process, and considering a crosslinkable functional group included in the acrylic resin. At the same time, a suitable kind of a known crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an acridine crosslinking agent and a metal chelating agent crosslinking agent can be used as a polyfunctional crosslinking agent. Examples of the isocyanate crosslinking agent may include a compound having at least two isocyanate groups, such as phenyl diisocyanate,
S -11 - 201202376 二異氰酸二甲酸苯酯、二異氰酸二苯基甲烷酯、二異氰酸 己二酯、二異氰酸異佛爾酮酯、二異氰酸四甲基二甲苯酯 或二異氰酸萘酯等或藉由令前述具有至少兩個異氰酸酯基 的化合物與多元醇（包括，例如，三羥甲基丙烷）反應而 得的交聯劑。此外’環氧基交聯劑可包括乙二醇二環氧丙 基醚、三環氧丙基醚、三羥甲基丙烷三環氧丙基醚、 N,N，N’，N’-四環氧丙基乙二胺和/或甘油二環氧丙基醚： 吖啶交聯劑的例子包括N，N’-甲苯-2,4-雙（1-吖啶羧醯胺 )、1^少’-二苯基甲烷-4,4’-雙（1-吖啶羧醯胺）、三伸乙 基三聚氰胺、雙異酞醯基-1-(2-甲基吖啶）和/或三-1-吖啶基膦化氧，但不在此限。金屬鉗合劑交聯劑的例子包 括多價金屬（如鋁、鐵、鋅、錫、鈦、銻、鎂或釩）配位 至乙醯基丙酮或乙醯乙酸的烷酯所形成之化合物等，但不 限於此。 相對於1〇〇重量份該丙烯酸系樹脂，該壓感黏合劑組 成物或IPN結構之該交聯劑的量可爲0.01至10重量份，更 佳爲0.01至5重量份。此範圍內，可極佳地維持壓感黏合 劑的黏合力和耐久性。 除了交聯該丙烯酸系樹脂而體現的交聯結構以外，該 壓感黏合劑組成物可另包含光可聚合的化合物作爲用以體 現他種交聯結構之組份。即，該IPN結構可另包含包含了 聚合的光可聚合化合物之交聯結構。此交聯結構可藉由將 光可聚合的化合物調合至壓感黏合劑組成物中及令光可聚 合的化合物經由照光而在硬化該組成物的程序中聚合的方 -12- 201202376 式體現。“光可聚合的化合物”是指分子結構中含有至少兩 個光可聚合的官能基之化合物，藉此，其可經由照光而聚 合以體現交聯結構。此外，該光可聚合的官能基係可藉照 光而聚合或交聯的官能基，且其例子包括包含乙烯系不飽 和雙鍵的官能基，如丙烯醯基或甲基丙烯醯基，但不限於 此。 可以使用，例如，多官能性丙烯酸酯（MFA )作爲該 光可聚合的化合物。 多官能性丙烯酸酯的例子可包括二官能性丙烯酸酯， 如二（甲基）丙烯酸1，4-丁二醇酯、二（甲基）丙烯酸 1，6-己二醇酯、二（甲基）丙烯酸新戊二醇酯、聚二（甲 基）丙烯酸乙二醇酯、二（甲基）丙烯酸新戊二醇己二酯 '二（甲基）丙烯酸羥基三甲基乙酸新戊二醇酯、二（甲 基）丙烯酸二環戊酯、經己內酯改質的二（甲基）丙烯酸 二環戊烯酯、經環氧乙烷改質的二（甲基）丙烯酸酯、異 氰尿酸二（甲基）丙烯醯氧基乙酯、烯丙基化的二（甲基 )丙烯酸環己酯、（甲基）丙烯酸三環癸烷二甲醇酯、二 (甲基）丙烯酸三羥甲基二環戊烷酯、經環氧乙烷改質的 二（甲基）丙烯酸六氫酞酸酯、（甲基）丙烯酸三環癸烷 二甲醇酯、經新戊二醇改質的二（甲基）丙烯酸三甲基丙 烷酯、二（甲基）丙烯酸金剛烷酯或9,9-雙[4- (2-丙烯醯 氧基乙氧基）苯基]莽；三官能性丙烯酸酯’如三（甲基 )丙烯酸三羥甲基丙烷酯、三（甲基）丙烯酸二季戊四醇 酯、經丙酸改質的三（甲基）丙烯酸二季戊四醇酯、三（ -13- 201202376 甲基）丙烯酸季戊四醇酯、經環氧丙烷改質的三（甲基） 丙烯酸三羥甲基丙烷酯、3-官能性（甲基）丙烯酸胺甲酸 酯或參（甲基）丙烯醯氧基乙基異氰尿酸酯；四官能性丙 烯酸酯，如四（甲基）丙烯酸二甘油酯或四（甲基）丙烯 酸季戊四醇酯；五官能性丙烯酸酯，如經丙酸改質的五（ 甲基）丙烯酸二季戊四醇酯；和六官能性丙烯酸酯，如六 (甲基）丙烯酸二季戊四醇酯、經己內酯改質的六（甲基 )丙烯酸二季戊四醇酯或（甲基）丙烯酸胺甲酸酯（如， 異氰酸酯單體和三（甲基）丙烯酸三羥甲基丙烷酯之反應 物），其中的一或至少二者可以單獨使用或併用，但不限 於此。 就耐久性觀之，較佳地，此處特別使用分子量低於 1，000且至少三官能性（即，至少3個（甲基）丙烯醯基） 的丙烯酸酯，但不限於此。 此外，較佳地，使用分子結構中包含環狀結構和/或 胺甲酸酯鍵的丙烯酸酯作爲多官能性丙烯酸酯。此情況中 ，丙烯酸酯中含括的環狀結構係任何碳環結構或雜環結構 ;或單環或多環結構。特別地，該多官能性丙烯酸酯中含 括的環狀結構可包括具3至12個碳原子（較佳3至8個碳原 子）的環烷基環狀結構，如環戊烷、環己烷或環庚烷，其 中的至少一者，較佳1至5者，更佳1至3者，含括於丙烯酸 酯中，且至少一個雜原子（如〇、S或N)亦含括於其中。 前述包含環狀結構和/或胺甲酸酯鍵的多官能性丙烯 酸酯的特定例子包括具有異氰尿酸酯結構的單體’如參（ -14- 201202376 甲基）丙烯醯氧基異氰尿酸乙酯；丙烯酸胺甲酸酯（如， 分子中具有環狀結構的異氰酸酯化合物（例如，異氰酸異 佛爾酮酯）和丙烯酸酯化合物（例如，三（甲基）丙烯酸 三羥甲基丙烷酯或三（甲基）丙烯酸季戊四醇酯）之反應 物等）等，但不限於此。 相對於1 〇〇重量份該丙烯酸系樹脂，該壓感黏合劑組 成物或IPN結構中之光可聚合的化合物之含量可爲1至30重 量份，較佳爲3至25重量份，更隹爲8至25重量份，又更佳 爲10至20重量份，藉此，可以有效地體現IPN結構，極佳 地維持於低和高速率的剝除力及安定地確保壓感黏合劑的 耐久性。 此外，此壓感黏合劑組成物可另包含光引發劑。該光 引發劑可藉照光而進行前述光可聚合的化合物之聚合反應 以提供壓感黏合劑內部的交聯結構。 光引發劑未特別限於任何種類。光引發劑的特定例子 包括苯偶因、羥基酮、胺基酮或膦化氧等，且更特別爲， 苯偶因、苯偶因甲醚、苯偶因***、苯偶因異丙醚、苯偶 因正丁醚、苯偶因異丁醚、苯乙酮、二甲胺基苯乙酮、 2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮 、2·羥基-2-甲基-1-苯丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲基硫）苯基]-2-嗎啉基-丙-1-酮' 4- ( 2-羥 基乙氧基）苯基-2-(羥基-2-丙基）酮、二苯基酮' 對-苯 基二苯基酮、4，4’-二乙胺基二苯基酮、二氯二苯基酮、2-甲基蒽醌、2-乙基蒽醌、2-三級丁基蒽醌、2-胺基蒽醌、 -15- 201202376 2-甲基-9·氧硫喔、2-乙基-9-氧硫喔、2-氯-9-氧硫喔、 2,4 -二甲基·9-氧硫喔、2,4 -二乙基-9-氧硫喔、苄基二甲縮 酮、苯乙酮二甲縮酮、對-二甲胺基苯甲酸酯、低聚[2 -羥 基-2-甲基-1-[4-(1-甲基乙烯基）苯基]丙酮]和2,4,6-三甲 基苄醯基-二苯基-膦化氧等，但不限於此。此處，可使用 前述之一或二或更多者。 相對於100重量份該光可聚合的化合物，光引發劑含 量爲0.1至10重量份，較佳爲〇.5至10重量份，且更佳爲0.5 至5重量份。若光引發劑的含量過低，則聚合反應或硬化 反應將無法順利進行。若含量過高，則物理性質（如耐久 可靠性或透光性）將有降低之虞。 壓感黏合劑組成物可另包含抗靜電劑，其中可以使用 任何化合物作爲抗靜電劑，只要其與組成物中含括的其他 組份（如丙烯酸系樹脂）的相容性極佳且提供壓感黏合劑 靜電性能’不會對其透光性、加工性和耐久性等造成不利 影響即可。抗靜電劑的例子可包括無機鹽或有機鹽等。 該無機鹽可爲包含鹼金屬陽離子或鹼土金屬陽離子作 爲陽離子組份的鹽。該陽離子的特定例子包括鋰離子（ Li+)、鈉離子（Na+)、鉀離子（Κ+)、鉚離子（Rb+) 、鉋離子（Cs+ )、鈹離子（Be2+ )、鎂離子（Mg2+ )、 鈣離子（Ca2+ )、緦離子（Sr2+ )和鋇離子（Ba2+ )等中 之一或二或更多者，就離子安定性和在壓感黏合劑中之移 動性觀之’較佳者爲鋰離子（Li+)、鈉離子（Na+)、鉀 離子（K+)、鉋離子（Cs+)、鈹離子（Be2+)、鎂離子 -16- 201202376 (Mg2+)、鈣離子（Ca2+)和鋇離子（Ba2+)中之一或二 或更多者，且最佳者爲鋰離子（Li+)，但不限於此。 此外，該有機鹽可爲包含鑰陽離子作爲陽離子組份的 鹽。“鑰陽離子”是指電荷的至少一部分定域於選自氮（N )、磷（P)和硫（S)中之至少一種原子之帶正（+)電 的離子。該鑰陽離子可爲環狀或非環狀化合物，其中該環 狀化合物可爲非芳族或芳族化合物。此外，該環狀化合物 可含有至少一個氮 '磷或硫原子以外的雜原子（如氧）。 該環狀或非環狀化合物亦可選擇性地經取代基（如氫、烷 基或芳基）取代。此外，該非環狀化合物可包含至少一個 ，較佳地，至少四個取代基，其中該取代基可爲環狀或非 環狀取代基或芳族或非芳族取代基。 一個特點中，該鑰陽離子可爲含氮的陽離子，較佳地 ，銨離子。該銨離子可爲四級銨離子或芳族銨離子。 較佳地，該四級銨離子特定爲以下列化學式2表示的 陽離子。 [化學式2]S -11 - 201202376 Diphenyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl diisocyanate A toluene ester or a naphthyl diisocyanate or the like or a crosslinking agent obtained by reacting a compound having at least two isocyanate groups described above with a polyol (including, for example, trimethylolpropane). Further, the 'epoxy crosslinking agent may include ethylene glycol diepoxypropyl ether, triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, N, N, N', N'-four Epoxypropylethylenediamine and/or glycerol diglycidyl ether: Examples of acridine crosslinking agents include N,N'-toluene-2,4-bis(1-acridinecarboxamide), 1^ Less '-diphenylmethane-4,4'-bis(1-acridinecarboxamide), tri-ethyl melamine, diisodecyl-1-(2-methylacridine) and/or three 1-Acridinylphosphine oxide, but not limited to this. Examples of the metal chelating agent crosslinking agent include compounds in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, ruthenium, magnesium or vanadium is coordinated to an alkyl ester of acetonitrile or acetonitrile, and the like. But it is not limited to this. The amount of the crosslinking agent of the pressure-sensitive adhesive composition or the IPN structure may be from 0.01 to 10 parts by weight, more preferably from 0.01 to 5 parts by weight, per part by weight of the acrylic resin. Within this range, the adhesion and durability of the pressure-sensitive adhesive are excellently maintained. In addition to the crosslinked structure exemplified by crosslinking the acrylic resin, the pressure-sensitive adhesive composition may further contain a photopolymerizable compound as a component for exhibiting a crosslinked structure. That is, the IPN structure may further comprise a crosslinked structure comprising a polymerized photopolymerizable compound. The crosslinked structure can be represented by the method of blending a photopolymerizable compound into a pressure-sensitive adhesive composition and polymerizing a photopolymerizable compound by illuminating in a procedure for hardening the composition. The "photopolymerizable compound" means a compound having at least two photopolymerizable functional groups in a molecular structure, whereby it can be polymerized by irradiation to exhibit a crosslinked structure. Further, the photopolymerizable functional group is a functional group which can be polymerized or crosslinked by light, and examples thereof include a functional group containing an ethylenically unsaturated double bond, such as an acryloyl group or a methacryloyl group, but not Limited to this. As the photopolymerizable compound, for example, a polyfunctional acrylate (MFA) can be used. Examples of the polyfunctional acrylate may include a difunctional acrylate such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, di(methyl) ) neopentyl glycol acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hexamethylene di(meth) acrylate hydroxytrimethyl acetic acid neopentyl glycol di(meth)acrylate , dicyclopentanyl (meth)acrylate, dicyclopentenyl di(meth)acrylate modified with caprolactone, di(meth)acrylate modified with ethylene oxide, isocyanuric acid Di(methyl)propenyloxyethyl ester, allylated cyclohexyl (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, trimethylol di(meth)acrylate Dicyclopentane ester, ethylene oxide modified di(meth)acrylic acid hexahydrophthalate, tricyclodecane dimethanol (meth)acrylate, neopentyl glycol modified di(a) Trimethylpropane acrylate, adamantyl di(meth)acrylate or 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene; Trifunctional acrylates such as trimethylolpropane tris(meth)acrylate, dipentaerythritol tris(meth)acrylate, dipentaerythritol tris(meth)acrylate modified by propionic acid, three (-13) - 201202376 Pentaerythritol (meth) acrylate, trimethylolpropane tris(meth)acrylate modified with propylene oxide, 3-functional (meth) acrylate or dimethyl (meth) acrylate Oxyethylethyl isocyanurate; tetrafunctional acrylate such as diglyceryl tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; pentafunctional acrylate such as five modified by propionic acid Dipentaerythritol (meth)acrylate; and hexafunctional acrylate such as dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate or amine (meth) acrylate modified by caprolactone A formate (for example, a reaction of an isocyanate monomer and trimethylolpropane tri(methyl)acrylate), one or at least two of which may be used alone or in combination, but is not limited thereto. In view of durability, it is preferred to use an acrylate having a molecular weight of less than 1,000 and at least trifunctional (i.e., at least 3 (meth)acryl fluorenyl), but is not limited thereto. Further, preferably, an acrylate having a cyclic structure and/or a urethane bond in the molecular structure is used as the polyfunctional acrylate. In this case, the cyclic structure included in the acrylate is any carbocyclic or heterocyclic structure; or a monocyclic or polycyclic structure. In particular, the cyclic structure included in the polyfunctional acrylate may include a cycloalkyl cyclic structure having 3 to 12 carbon atoms (preferably 3 to 8 carbon atoms), such as cyclopentane or cyclohexane. Alkane or cycloheptane, at least one of which is preferably from 1 to 5, more preferably from 1 to 3, is included in the acrylate, and at least one hetero atom (such as ruthenium, S or N) is also included among them. Specific examples of the aforementioned polyfunctional acrylate comprising a cyclic structure and/or a urethane bond include a monomer having an isocyanurate structure such as ginseng (-14-201202376 methyl) propylene oxirane isocyanide Ethyl urate; urethane acrylate (eg, an isocyanate compound having a cyclic structure in the molecule (for example, isophorone isocyanate) and an acrylate compound (for example, trishydroxymethyltris(meth)acrylate) The reaction product of propane ester or pentaerythritol tri(meth)acrylate), etc., but is not limited thereto. The content of the photopolymerizable compound in the pressure-sensitive adhesive composition or the IPN structure may be 1 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 1 part by weight per part by weight of the acrylic resin. It is 8 to 25 parts by weight, and more preferably 10 to 20 parts by weight, whereby the IPN structure can be effectively embodied, the peeling force at a low and high rate is excellently maintained, and the durability of the pressure-sensitive adhesive is ensured stably. Sex. Additionally, the pressure sensitive adhesive composition may additionally comprise a photoinitiator. The photoinitiator can carry out the polymerization of the aforementioned photopolymerizable compound by light to provide a crosslinked structure inside the pressure sensitive adhesive. The photoinitiator is not particularly limited to any kind. Specific examples of the photoinitiator include benzoin, hydroxyketone, aminoketone or phosphine oxide, and more particularly, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, Benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 2·hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methyl Thio)phenyl]-2-morpholinyl-propan-1-one' 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, diphenyl ketone 'p- Phenyldiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, dichlorodiphenyl ketone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tributyl fluorene , 2-amino hydrazine, -15- 201202376 2-methyl-9 oxa thiopurine, 2-ethyl-9-oxopurine, 2-chloro-9-oxathione, 2,4-dimethyl 9-oxopurine, 2,4-diethyl-9-oxopurine, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoate, oligomerization [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] and 2,4,6-trimethylbenzylidene- Phenyl - phosphine oxide and the like, but is not limited thereto. Here, one or two or more of the foregoing may be used. The photoinitiator is contained in an amount of from 0.1 to 10 parts by weight, preferably from 0.5 to 10 parts by weight, and more preferably from 0.5 to 5 parts by weight, per 100 parts by weight of the photopolymerizable compound. If the content of the photoinitiator is too low, the polymerization reaction or the hardening reaction will not proceed smoothly. If the content is too high, physical properties such as durability reliability or light transmission will be lowered. The pressure-sensitive adhesive composition may further contain an antistatic agent, and any compound may be used as the antistatic agent as long as it has excellent compatibility with other components (for example, acrylic resin) included in the composition and provides pressure. The electrostatic properties of the adhesive can't adversely affect its light transmission, processability and durability. Examples of the antistatic agent may include inorganic salts or organic salts and the like. The inorganic salt may be a salt containing an alkali metal cation or an alkaline earth metal cation as a cationic component. Specific examples of the cation include lithium ion (Li+), sodium ion (Na+), potassium ion (Κ+), riveting ion (Rb+), planing ion (Cs+), barium ion (Be2+), magnesium ion (Mg2+), calcium. One or two or more of ions (Ca2+), strontium ions (Sr2+), and barium ions (Ba2+), etc., in terms of ion stability and mobility in pressure-sensitive adhesives, the preferred one is lithium ion. (Li+), sodium ion (Na+), potassium ion (K+), planer ion (Cs+), barium ion (Be2+), magnesium ion-16-201202376 (Mg2+), calcium ion (Ca2+) and barium ion (Ba2+) One or two or more, and the most preferred one is lithium ion (Li+), but is not limited thereto. Further, the organic salt may be a salt containing a key cation as a cationic component. "Key cation" means that at least a portion of the charge is localized to positive (+) charged ions of at least one atom selected from the group consisting of nitrogen (N), phosphorus (P), and sulfur (S). The key cation may be a cyclic or acyclic compound, wherein the cyclic compound may be a non-aromatic or aromatic compound. Further, the cyclic compound may contain at least one hetero atom other than nitrogen 'phosphorus or a sulfur atom (e.g., oxygen). The cyclic or acyclic compound may also be optionally substituted with a substituent such as hydrogen, an alkyl group or an aryl group. Furthermore, the acyclic compound may comprise at least one, preferably at least four substituents, wherein the substituent may be a cyclic or acyclic substituent or an aromatic or non-aromatic substituent. In one feature, the key cation can be a nitrogen-containing cation, preferably an ammonium ion. The ammonium ion can be a quaternary ammonium ion or an aromatic ammonium ion. Preferably, the quaternary ammonium ion is specifically a cation represented by the following Chemical Formula 2. [Chemical Formula 2]
Rq—n~R7 r8 其中，116至r9各者獨立地代表氫；經取代或未經取代 的烷基；經取代或未經取代的烷氧基；經取代或未經取代 的烯基；經取代或未經取代的炔基；經取代或未經取代的 芳基；或經取代或未經取代的雜芳基。 -17- 201202376 該化學式2的定義中，烷基或烷氧基可代表具1至丨2個 碳原子（較佳1至8個碳原子）的烷基或烷氧基，而烯基或 炔基可代表具2至12個碳原子（較佳2至8個碳原子）的烯 基或炔基。 此外，在該化學式2的定義中，芳基代表苯基、聯苯 基、萘基或蒽環系統等，作爲由芳族化合物衍生的取代基 :雜芳基是指含有至少一個雜原子（選自0、N和S)的5 至12員雜環或芳環且特定言之，代表呋喃基、吡咯基、吡 咯烷基、噻嗯基、吡啶基、哌啶基、吲哚基、喹啉基、噻 唑基、苯并噻唑基和***基等。 此外，該化學式2的定義中，烷基、烷氧基、烯基、 炔基、芳基或雜芳基可經至少一個取代基取代，其中取代 基的例子可包括羥基、鹵素、或具1至12個碳原子（較佳1 至8個碳原子，更佳1至4個碳原子）的烷基或烷氧基，但 不限於此。 本發明中，較佳使用該化學式2之陽離子的四級銨陽 離子，且特別是其中心至R4各者獨立地爲具1至12個碳原 子（較佳1至8個碳原子）之經取代或未經取的烷基之陽離 子。 化學式2代表之該四級銨離子的特定例子可包括N-乙 基-N，N-二甲基-N-(2-甲氧基乙基）銨離子、N，N-二乙基-N -甲基-N-(2 -甲氧基乙基）銨離子、N -乙基-Ν,Ν-二甲 基-Ν-丙基銨離子、Ν-甲基-Ν，Ν，Ν-三辛基銨離子、Ν，Ν，Ν-三甲基-Ν-丙基銨離子、四丁基銨離子、四甲基銨離子、 -18- 201202376 四己基銨離子和N-甲基-N，N，N-三丁基銨離子等，但不限 於此》 此外，該芳族銨離子的例子可包括選自吡啶陽離子、 吡哄陽離子、嘧啶陽離子、哌啶陽離子、咪唑陽離子、哌 唑陽離子、噻唑陽離子、噁唑陽離子和***陽離子中之一 或多者，且較佳爲經具4至16個碳原子的烷基取代之N-烷 基吡啶陽離子、經具2至10個碳原子的烷基取代之1，3 -烷 基甲基咪唑陽離子和經具2至10個碳原子的烷基取代之 1，2_二甲基-3-烷基咪唑陽離子中之一或至少二者，但不限 於此。 該芳族銨離子亦可爲以下列化學式3表示的化合物。 [化學式3]Rq—n~R7 r8 wherein each of 116 to r9 independently represents hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group. -17- 201202376 In the definition of the chemical formula 2, an alkyl group or an alkoxy group may represent an alkyl group or alkoxy group having 1 to 2 carbon atoms (preferably 1 to 8 carbon atoms), and an alkenyl group or an alkyne group The group may represent an alkenyl or alkynyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Further, in the definition of the chemical formula 2, the aryl group represents a phenyl group, a biphenyl group, a naphthyl group or an anthracene ring system, etc., as a substituent derived from an aromatic compound: a heteroaryl group means at least one hetero atom (selected 5- to 12-membered heterocyclic or aromatic rings from 0, N and S) and, in particular, furanyl, pyrrolyl, pyrrolidinyl, thienyl, pyridyl, piperidinyl, fluorenyl, quinoline Base, thiazolyl, benzothiazolyl and triazolyl, and the like. Further, in the definition of the chemical formula 2, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group may be substituted with at least one substituent, and examples of the substituent may include a hydroxyl group, a halogen, or have 1 An alkyl group or alkoxy group of up to 12 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms), but is not limited thereto. In the present invention, the quaternary ammonium cation of the cation of the chemical formula 2 is preferably used, and in particular, the center to R4 are each independently substituted with 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms). Or a cation of an alkyl group that has not been taken. Specific examples of the quaternary ammonium ion represented by Chemical Formula 2 may include N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium ion, N,N-diethyl-N -methyl-N-(2-methoxyethyl)ammonium ion, N-ethyl-hydrazine, Ν-dimethyl-Ν-propyl ammonium ion, Ν-methyl-Ν, Ν, Ν-three Octyl ammonium ion, hydrazine, hydrazine, hydrazine-trimethyl-hydrazine-propyl ammonium ion, tetrabutylammonium ion, tetramethylammonium ion, -18-201202376 tetrahexylammonium ion and N-methyl-N, N,N-tributylammonium ion or the like, but is not limited thereto. Further, examples of the aromatic ammonium ion may include a pyridinium cation, a pyridinium cation, a pyrimidine cation, a piperidine cation, an imidazolium cation, a piperazine cation, One or more of a thiazole cation, an oxazole cation, and a triazole cation, and preferably an N-alkylpyridine cation substituted with an alkyl group having 4 to 16 carbon atoms, having 2 to 10 carbon atoms One or at least two of an alkyl-substituted 1,3 -alkylmethylimidazolium cation and a 1,2-dimethyl-3-alkylimidazolium cation substituted with an alkyl group having 2 to 10 carbon atoms, But it is not limited to this. The aromatic ammonium ion may also be a compound represented by the following Chemical Formula 3. [Chemical Formula 3]
其中，Rig至R15各者獨立地代表氫：經取代或未經取 代的烷基；經取代或未經取代的烷氧基；經取代或未經取 代的烯基；經取代或未經取代的炔基；經取代或未經取代 的劳基；或經取代或未經取代的雜芳基。 該化學式3中，烷基、烷氧基、烯基、炔基 '芳基和 雜芳基之定義及它們的取代基與該化學式2中者相同。 該化學式3的化合物中，特別佳的化合物中，R,,至 -19- 201202376 R15各者獨立地爲氫或烷基，而Rio爲烷基。 本抗靜電劑中，含有該陽離子之無機或有機鹽中含括 之陰離子的例子較佳選自氟（F·)、氯（Cl_ )、溴（Br_ )、碘（Γ)、過氯酸（C104_ )、氫氧化物（OH_ )、碳 酸（C032·)、硝酸（ΝΟΓ)、磺酸（S〇r)、甲基苯磺 酸（ch3(c6h4) so3·)、對甲基苯磺酸（ch3c6h4so3_ )、羧基苯磺酸（COOH(C6H4)S〇r)、三氟甲磺酸（ CF3S02_)、苯酸（C6H5COO_)、乙酸（CH3COO·)、三 氟乙酸（CF3COO_)、四氟硼酸（BF4·)、四苄基硼酸（ b(c6h5)4_)、六氟磷酸（pf6_)、參五氟乙基三氟磷酸 (P ( C2F5 ) 3F3·)、雙三氟甲磺醯亞胺（N ( S02CF3 ) 2-)、雙五氟乙磺醯亞胺（N(SOC2F5)r)、雙五氟乙烷 羰醯亞胺（N ( COC2F5 )2_)、雙全氟丁烷磺醯亞胺（N (S02C4F9) 2_)、雙全氟丁烷羰醯亞胺（N ( COC4F9) 2_ )、參三氟甲烷磺醯基甲基化物（C(S02CF3)3·)、和 參三氟甲烷羰基甲基化物（C( C02CF3 ) 3·)，但不限於 此。該陰離子中，較佳使用醯亞胺陰離子，其提供較佳拉 電子效果且經具有良好疏水性的氟取代而具有高離子安定 性，但不限於此。 相對於1 00重量份壓感黏合劑組成物中的丙烯酸系樹 脂，此抗靜電劑含量可爲0.01至5重量份，較佳爲0.01至2 重量份，且更佳爲0.1至2重量份。若該量低於0.01重量份 ，則將無法得到所欲抗靜電效果。若超過5重量份，則由 於與其他組份的相容性變低，所以將損及壓感黏合劑的耐 -20- 201202376 久可靠性或透光性。 除了前述組份以外，本壓感黏合劑組成物可另包含能 夠與該抗靜電劑（特定言之，含括於其中的陽離子）形成 配位鍵的化合物（下文中，選擇性地稱爲“配位鍵化合物” )。若適當地含括此配位鍵化合物，則即使使用相當少量 的抗靜電劑，壓感黏合劑中之陰離子濃度提高可有效地提 供抗靜電效能。 此處可用的配位鍵化合物未特別限於任何類型，只要 其具有能夠在分子中配位鍵結的官能基即可。 例如，此處可以使用伸烷化氧化合物作爲該配位鍵化 合物。 雖然此處可使用的伸烷化氧化合物未特別限於任何種 類，較佳地，使用包含其基礎單元具有至少二（較佳3至 12，更佳3至8)個碳原子的伸烷化氧單元之伸烷化氧化合 物。 此外，較佳地，此處的該伸烷化氧化合物之分子量爲 5,000或更低。此處的“分子量”是指化合物的分子量或重 量平均分子量。若伸烷化氧化合物的分子量超過5，000， 則因黏度過度提高，塗覆性將受損，或與金屬形成錯合物 的效能將降低。同時，未特別限制該伸烷化氧化合物中之 分子量的下限，且可適當地控制在，例如，500或更高， 較佳爲4,000或更高，的範圍內。 未特別限制此處可用的伸烷化氧鉗合劑的特定例子， 只要其展現前述特性即可。例如，可以使用下列化學式4 -21 - 17 201202376 表示的化合物。 [化學式4]Wherein each of Rig to R15 independently represents hydrogen: substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted Alkynyl; substituted or unsubstituted labor; or substituted or unsubstituted heteroaryl. In the Chemical Formula 3, the definitions of the alkyl group, the alkoxy group, the alkenyl group, the alkynyl 'aryl group and the heteroaryl group and the substituents thereof are the same as those in the Chemical Formula 2. Among the compounds of Chemical Formula 3, among the particularly preferred compounds, R, from -19 to 201202376 R15 are each independently hydrogen or an alkyl group, and Rio is an alkyl group. In the antistatic agent, examples of the anion contained in the inorganic or organic salt containing the cation are preferably selected from the group consisting of fluorine (F·), chlorine (Cl_), bromine (Br_), iodine (Γ), and perchloric acid ( C104_), hydroxide (OH_), carbonic acid (C032·), nitric acid (ΝΟΓ), sulfonic acid (S〇r), toluenesulfonic acid (ch3(c6h4) so3·), p-toluenesulfonic acid ( Ch3c6h4so3_), carboxybenzenesulfonic acid (COOH(C6H4)S〇r), trifluoromethanesulfonic acid (CF3S02_), benzoic acid (C6H5COO_), acetic acid (CH3COO.), trifluoroacetic acid (CF3COO_), tetrafluoroboric acid (BF4) ·), tetrabenzylboronic acid (b(c6h5)4_), hexafluorophosphoric acid (pf6_), pentafluoroethyltrifluorophosphate (P(C2F5)3F3·), bistrifluoromethanesulfonimide (N ( S02CF3) 2-), bispentafluoroethanesulfonimide (N(SOC2F5)r), bispentafluoroethane carbodiimide (N (COC2F5)2_), diperfluorobutane sulfonimide (N ( S02C4F9) 2_), bisperfluorobutane carbonyl quinone imine (N (COC4F9) 2_ ), ginseng trifluoromethanesulfonyl methide (C(S02CF3)3·), and paratrifluoromethane carbonyl methide ( C(C02CF3) 3·), but is not limited to this. Among the anions, a quinone imine anion which preferably provides a preferred electron withdrawing effect and is substituted with fluorine having good hydrophobicity and has high ion stability is preferable, but is not limited thereto. The antistatic agent may be contained in an amount of from 0.01 to 5 parts by weight, preferably from 0.01 to 2 parts by weight, and more preferably from 0.1 to 2 parts by weight, per 100 parts by weight of the acrylic resin in the pressure-sensitive adhesive composition. If the amount is less than 0.01 parts by weight, the desired antistatic effect will not be obtained. If it exceeds 5 parts by weight, the compatibility with other components becomes low, so that the resistance of the pressure-sensitive adhesive is -20-201202376 long-term reliability or light transmittance. In addition to the foregoing components, the pressure-sensitive adhesive composition may further comprise a compound capable of forming a coordinate bond with the antistatic agent (specifically, a cation included therein) (hereinafter, alternatively referred to as " Coordination bond compound"). If the coordination bond compound is appropriately included, the increase in the anion concentration in the pressure-sensitive adhesive can effectively provide antistatic efficacy even when a relatively small amount of the antistatic agent is used. The coordination bond compound usable herein is not particularly limited to any type as long as it has a functional group capable of coordinate bonding in a molecule. For example, an alkylene oxide compound can be used herein as the coordination bond compound. Although the alkylene oxide compound which can be used herein is not particularly limited to any kind, it is preferred to use an alkylene oxide having at least two (preferably 3 to 12, more preferably 3 to 8) carbon atoms in its base unit. The alkylene oxide compound of the unit. Further, preferably, the alkylene oxide compound herein has a molecular weight of 5,000 or less. The "molecular weight" herein means the molecular weight or weight average molecular weight of the compound. If the molecular weight of the alkylene oxide compound exceeds 5,000, the coating property is impaired due to an excessive increase in viscosity, or the effect of forming a complex compound with a metal is lowered. Meanwhile, the lower limit of the molecular weight in the alkylene oxide compound is not particularly limited, and may be appropriately controlled within the range of, for example, 500 or more, preferably 4,000 or more. Specific examples of the alkylene oxide chelating agent usable herein are not particularly limited as long as they exhibit the aforementioned characteristics. For example, a compound represented by the following chemical formula 4-21- 17 201202376 can be used. [Chemical Formula 4]
R 其中’ Α代表具有至少2個碳原子的伸烷基，„是1至 120 ’ R1(i和各者獨立地代表氫、羥基、烷基或_c ( =〇 )Ri8’其中Rl8代表氫或烷基。 該化學式4的定義中，伸烷基代表具3至12(較佳3至8 )個碳原子的伸烷基，且特定言之爲伸乙基' 伸丙基、伸 丁基或伸戊基。 此外’在化學式4的定義中，烷基代表具1至12 (較佳 1至8’更佳1至4)個碳原子的烷基，而n代表較佳1至80, 更佳1至4 0。 化學式4代表的化合物的特定例子可包括聚伸烷化氧 (如聚伸乙化氧、聚伸丙化氧、聚伸丁化氧或聚伸戊化氧 等）、.聚伸烷化氧（如聚伸乙化氧、聚伸丙化氧、聚伸丁 化氧或聚伸戊化氧等）的脂肪酸烷酯或聚伸烷化氧（如聚 伸乙化氧、聚伸丙化氧、聚伸丁化氧或聚伸戊化氧等）的 羧酸酯，但不限於此》 此處，除了前述伸烷化氧化合物以外，必要時，可以 適當地選擇和使用各式各樣的配位化合物，如分子中具有 至少一個醚鍵的酯化合物（述於KR專利申請公告第2006-0018495號）、含有草酸基的化合物（述於KR專利申請公 告第2006-0128695號）、含有二胺基的化合物、含有多竣 -22- 201202376 基的化合物或含有酮基的化合物。 相對於100重量份的丙烯酸系樹脂，該配位化合物在 壓感黏合劑組成物中的含量可高至3重量份，較佳爲0.1至 3重量份，且更佳爲0.5至2重量份。若該量超過3重量份， 則將有物理性質（如剝除力）降低之虞。 該壓感黏合劑組成物可另包含矽烷偶合劑。例如，此 矽烷偶合劑可包括γ-縮水甘油醚基丙基三乙氧基矽烷、γ· 縮水甘油醚基丙基三甲氧基矽烷、γ -縮水甘油醚基丙基甲 基二乙氧基矽烷、γ-縮水甘油醚基丙基三乙氧基矽烷、3-毓丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙 氧基矽烷、γ-甲基丙烯醯氧基三甲氧基矽烷、γ-甲基丙烯 醯氧基丙基三乙氧基矽烷、γ-胺丙基三甲氧基矽烷、γ-胺 丙基三乙氧基矽烷、3-異氰酸基丙基三乙氧基矽烷、γ-乙 醯乙酸丙基三甲氧基矽烷、γ·乙醯乙酸丙基三乙氧基矽烷 、β-氰基乙醯基三甲氧基矽烷、β·氰基乙醯基三乙氧基矽 烷、和乙醯氧基乙醯基三甲氧基矽烷，其中的一或至少二 者可單獨使用或併用。此處，較佳使用具有乙醯乙酸基或 β-氰基乙醯基的矽烷偶合劑，但不限於此。本組成物中， 相對於1〇〇重量份丙烯酸系樹脂，矽烷偶合劑含量可爲 0.01至5重量份，較佳爲0.01至1重量份。若偶合劑含量低 於0.01重量份，則提高黏合強度的效果微弱。若超過5重 量份，則耐久可靠性將降低。 就控制黏合性能觀之，此壓感黏合劑組成物可另包含 發黏樹脂。此發黏樹脂未限於任何種類。例如，可使用烴 -23- 201202376 樹脂或其氫化產物、松香樹脂或其氫化產物、松香酯樹脂 或其氫化產物、萜烯樹脂或其氫化產物、萜烯酚樹脂或其 氫化產物、聚合的松香樹脂或聚合的松香酯樹脂中之一或 至少二者之混合物。相對於100重量份丙烯酸系樹脂，該 發黏樹脂含量爲1至100重量份。若該量低於1重量份，則 其添加效果微弱。若其量超過100重量份，則增進相容性 和/或黏合力的效果將降低。 在不影容本發明之效果的範圍內，此壓感黏合劑組成 物可另包含至少一種選自環氧樹脂、交聯劑、紫外光安定 劑、抗氧化劑、著色劑、強化劑、塡料、抗起泡劑、界面 活性劑和塑化劑之添加劑。 該壓感黏合劑組成物於硬化之後，即，包含IPN結構 的狀態，的凝膠比例爲80%至99%。此處，凝膠比例係藉 下列通式1計算得到的値》 [通式1] 凝膠比例= B/ A X 100 其中，A代表體現IPN結構之壓感黏合劑組成物的質 量，而B代表在前述相同的壓感黏合劑組成物於室溫在乙 酸乙酯中澱積48小時之後，回收之不溶物的乾重。 在前述範圍內的壓感黏合劑可以有效地維持於低和高 速率之剝除力特性。 在固化之後，即，於包含1PN結構的狀態’此壓感黏 -24- 201202376 合劑組成物的低速率剝除力（X!)爲8至40克力/英吋， 而高速率剝除力（X2 )爲80至3 00克力/英吋。“低速率剝 除力”是指於剝除角度180°和剝除速率0.3米/分鐘測定時 ，對TAC片的剝除力（X!)，且特定言之，係根據下列測 定方法2中指定的方法測得的剝除力。此外，“高速率剝除 力”是指於剝除角度180°和剝除速率30米/分鐘測定時， 對TAC片的剝除力（Χ2 )，且特定言之，係根據下列測定 方法2中指定的方法測得的剝除力。 低速率剝除力（X!)較佳爲1 0至3 0克力/英吋，更佳 爲1 0至2 0克力/英吋。藉由將低速率剝除力（X i )控制於 該範圍內，所提供的壓感黏合劑安定地保護光學元件使其 免於污染且不會因爲剝除黏合劑而受損。 此外，高速率剝除力（x2)較佳爲100至280克力/英 吋，更佳爲100至2 00克力/英吋，又更佳爲1〇〇至150克力 /英吋。藉由將高速率剝除力控制於該範圍內，不會因爲 高速率剝除程序而損及被黏合物，並有效抑制靜電力之類 發生。 此外，該高速率剝除力（X2)對低速率剝除力（Xj) 的比値，即，x2/x,，可爲1至15，較佳爲5至15，且更佳 爲7至13。藉由將該比値（Χζ/Χ,)控制於1至15的範圍內 ’黏合劑能夠有效地於剝除時脫離，提供作爲光學元件之 保護膜的極佳保護作用。 本發明亦係關於一種用於光學元件的保護膜，其包含 壓感黏合層’該壓感黏合層包含互相貫穿的聚合物網絡結 -25- 201202376 構，該結構具有在交聯狀態之重量平均分子. 1，1 00,000或更低的丙烯酸系樹脂，且，其於剝除角度 和剝除速率0.3米/分鐘測定時，對TAC片的剝除力;| 40克力/英吋；及於剝除角度180°和剝除速率30米/ 測定時，對TAC片的剝除力爲80至300克力/英吋。 該保護膜的壓感黏合層可藉由令根據本發明之前 感黏合劑組成物硬化而形成。因此，該壓感黏合層中 的個別組份，或於低和高速率測定該壓感黏合劑之剝 (X,、X2 )的特定方法或値等與關於該壓感黏合劑組 之描述相同。 此外，該用於光學元件之保護膜可以，例如，另 基板，其中壓感黏合層形成於該基板的一或兩面上。 述者，藉由令該壓感黏合劑組成物硬化而形成的壓感 層於低速率具有高剝除力及於高速率具有低剝除力並 此二剝除力之間的良好平衡。此外，該壓感黏合層具 佳的耐久性、加工性、透光性和抗靜電性質》因此， 感黏合劑組成物可有效地施用至各式各樣的光學裝置 件，或顯示裝置或元件。一種壓感黏合板由透光基板 成；且形成於該透光基板上之根據本發明之該壓感黏 可以有效地作爲保護光學元件（如偏光板、阻滯板、 補償膜、反射片或亮光增進膜）的保護膜，其施用至 顯示裝置等。 但是，該保護膜可以有效地作爲各式各樣的工業 例如，保護膜、清潔片、反射片、結構壓感黏合片、 量爲 180° "至 分鐘 述壓 含括 除力 成物 包含 如前 黏合 具有 有極 該壓 或元 所組 合層 光學 液晶 片， 攝影 •26- 201202376 用的壓感黏合片、用以指出行車道的壓感黏合片、用於電 子元件的光學壓感黏合產品或壓感黏合劑，但不限於前述 用途。此外，根據本發明之丙烯酸系組成物可以有效地用 於多結構的層合產品、一般市售壓感黏合片產品、藥用貼 布、熱活化的壓感黏合劑等。 此領域中的一般透光膜可以無任何限制地作爲此保護 膜的基板，其例子包括塑膠膜，如聚酯膜（如聚對酞酸乙 二酯膜、聚對酞酸丁二酯膜）、聚四氟乙烯膜、聚乙烯膜 、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、 或聚醯胺膜。此基板膜可由單層或至少兩個層合層所組成 ，且選擇性地，另包含官能層，如防污層或抗靜電層。此 外，就增進黏合性觀之，可以在該基板的一或兩面上進行 表面處理（如底漆處理）。 取決於其用途，基板厚度經適當選擇且無特別的限制 ，其中基板厚度通常爲5至500微米，且較佳爲10至100微 米。 此外，未特別限制該壓感黏合層厚度，且可爲，例如 ，2至100微米，且較佳爲5至50微米。若壓感黏合層厚度 不在前述範圍內，則將會由於難以形成壓感黏合層，而使 得壓感黏合膜的物理性質不平均。 未特別限制形成該壓感黏合層之方法，例如，可以使 用藉由一般的方式（如棍塗覆機），將該壓感黏合劑組成 物或包含彼之液體施用至基板上等，及使其硬化之方法， 或先將壓感黏合劑組成物施用至可脫模基板之表面，使其 -27- 201202376 硬化，及之後轉移形成的壓感黏合層之方法。 此外，未特別限制在前述程序中，令壓感黏合劑組成 物硬化之方法，且，例如，可以經由適當的老化法進行， 使得丙烯酸系樹脂和交聯劑能夠反應，或照光（例如，紫 外光），其誘發可聚合的化合物之光聚合反應。該紫外光 照射可以使用如高壓汞燈、無電極燈或氙燈進行。同樣地 ，在紫外光硬化法中，未特別限制照射量，只要其控制至 得到足夠的硬化且不損及物理性質即可。例如，較佳地， 照度爲50至1，000毫瓦特/平方公分而光量爲50至1，〇〇〇毫 焦耳/平方公分。 本發明亦係關於光學元件，其包含基板：和附於該基 板之一或兩面的前述保護膜。 該基板可爲，例如，偏光板、阻滯板、光學補償膜、 反射片或亮光增進膜等，且通常爲偏光板，作爲可施用至 液晶顯示裝置的功能片。 該偏光板可具有，例如，包含偏光器之結構；和形成 於該偏光器之一或兩面上之用於偏光器的保護膜。此外， 選擇性地，本偏光板可另包含至少一個功能層，其選自保 護層、反射層、防眩光層、阻滞板、寬視角補償膜和亮光 增進膜。 偏光板中含括的偏光器未特別限於任何種類，且例如 ，可以無任何限制地採用一般種類，如此領域已知的聚乙 烯醇偏光器。 此偏光器係功能膜或片，其可自在數個方向震動的入 •28- 201202376 射光僅擷取在一個方向震動的光。此偏光器可爲，例如， 二向色經吸附並對準聚乙烯醇樹脂膜的形式。例如，構成 偏光器的聚乙烯醇樹脂可藉由令聚乙酸乙烯酯樹脂膠凝而 得到。此處，可用的聚乙酸乙烯酯樹脂可包括乙酸乙烯酯 和其他可與乙酸乙烯酯聚合的單體之共聚物，及乙酸乙烯 酯之均聚物。前述者中，可與乙酸乙烯酯聚合之單體的例 子可包括不飽和羧酸、烯烴、乙烯醚、具有銨基的不飽和 磺酸和丙烯醯胺中之一或至少二者、其組合，但不限於此 。聚乙烯醇之膠凝程度通常爲85至100莫耳。/。，較佳至少 9 8莫耳％。該聚乙烯醇樹脂亦可經額外改質，且例如，亦 可使用經醛改質的聚乙烯基甲縮醛和聚乙烯基乙縮醛。此 外，聚乙烯醇樹脂的聚合度通常爲1,000至10,000，較佳 爲 1，500至 5,000 » 前述聚乙烯醇樹脂可製成膜並以偏光器的碟膜形式使 用。未特別限制自聚乙烯醇樹脂形成膜的方法且可使用此 領域已知的一般方法。未特別限制聚乙烯醇樹脂形成之碟 膜的厚度，其可適當地控制在例如，1至150微米的範圍內 。考慮拉伸容易度，該碟膜的厚度可控制於至少10微米。 此偏光器可經由拉伸（如，單軸拉伸）前述聚乙烯醇 樹脂膜，以二向色令此聚乙烯醇樹脂膜染色並吸附於其中 ，以硼酸水溶液處理具有吸附的二向色之聚乙烯醇樹脂膜 ，及在以硼酸水溶液處理之後清洗，之方法製得。可以使 用碘或二向色有機染料等作爲二向色。 此外，此偏光板可另包含形成該偏光器之一或兩面上 -29- 201202376 的保護膜。該保護膜之槪念不同於前述包含根據本發明之 壓感黏合層的保護膜。可含括於本偏光板中之此保護膜未 特別限於任何種類，且可製成與由例如纖維素膜（如三乙 醯基纖維素）、聚酯膜（如聚碳酸酯膜或聚對酞酸乙二酯 膜）、聚醚楓膜、和/或聚烯烴膜（如聚乙烯膜、聚丙烯 膜或具有環或降莰烯結構的聚烯烴膜或聚烯烴膜（如乙烯 丙烯共聚物））等所組成之保護膜層合的多層膜形式。此 處，亦未特別限制該保護膜的厚度且其可形成具有一般厚 度者。 本發明亦係關於液晶顯示裝置，其包含液晶面板；附 在該液晶面板的一或兩面上之該光學元件，其中該光學元 件係通常附有該保護膜的偏光板。 含括於液晶顯示裝置中之裤晶面板未特別限於任何種 類。例如，可以使用所有的各式各樣惰性基質類型，包括 TN (扭曲向列）型、STN (超扭曲向列）型、F (鐵電） 型和PD(聚合物分散的LCD )型等；各式各樣的活性基質 型，包括二端點型和三端點型；已知液晶面板，包括同平 面切換（IPS)模式面板和直立對準（VA)模式面板。此 外’本發明之液晶顯示裝置中含括的其他組件未特別限於 任何種類’且亦未特別限制其製法。可以無限制地選擇和 使用此領域中的一般構件。 [有利的效果] 本發明可提供壓感黏合組成物和用於光學元件的保護 -30- 201202376 膜，其於低速率具有高剝除力及於高速率具有低剝除力， 其維持極佳平衡並展現對於被黏合物的極佳潤濕性、耐久 性、再貼附性、透光性和抗靜電效能。 [本發明之模式] 藉下列根據本發明之實例和非根據本發明之比較例更 詳細地解釋本發明，但本發明之範圍不限於下列實例。 製備例1:丙烯酸系樹脂（A1)之製備 在有氮氣迴流及配備冰箱以易於調整溫度的1升反應 器中，倒入98重量份丙烯酸2-乙基己酯（2-EHA)和2重 量份丙烯酸2-羥基丁酯（2-HBA)和作爲溶劑的100重量 份乙酸乙酯（EAc )。然後，通氮1小時以移除氧，且溫 度維持於62°C。之後，倒入0.03重量份反應引發劑，偶氮 基雙異丁腈（AIBN )，和0.05重量份分子量調整劑，正 十二碳烷基硫醇（n-D DM )，並反應8小時。反應之後， 反應物以乙酸乙酯（E Ac )稀釋以製得固體含量濃度爲44 重量％且重量平均分子量（Mw)爲450,0〇〇的丙烯酸系樹 脂（A 1 )。 製備例2:丙烯酸系樹脂（A2)之製備 在有氮氣迴流及配備冰箱以易於調整溫度的1升反應 器中，倒入97.5重量份丙烯酸丁酯（BA )和1.5重量份丙 烯酸2-羥基丁酯（2-HBA)和作爲溶劑的100重量份乙酸 -31 - 201202376 乙酯（EAc )。然後，通氮1小時以移除氧，且溫度維持 於62°C。之後，倒入〇.〇3重量份偶氮基雙異丁腈（AIBN )和0.05重量份正十二碳烷基硫醇（n-DDM )，反應8小 時並以乙酸乙酯（EAc)稀釋以製得固體含量濃度爲44重 量％且重量平均分子量（Mw)爲600,000的丙烯酸系樹脂 (A2 )。 製備例3:丙烯酸系樹脂（A3)之製備 在有氮氣迴流及配備冰箱以易於調整溫度的1升反應 器中，倒入99重量份丙烯酸2-乙基己酯（2-EHA)和1重 量份丙烯酸2-羥基丁酯（2-HBA)和作爲溶劑的100重量 份乙酸乙酯（EAc )、然後，通氮1小時以移除氧。反應 器中之溫度維持於60 °C時，倒入0.01重量份偶氮基雙異丁 腈（AIBN )，反應8小時並以乙酸乙酯（EAc )稀釋以製 得固體含量濃度爲44重量％且重量平均分子量（Mw)爲 1，200,000的丙烯酸系樹脂（A3)。 製備例4:丙烯酸系樹脂（A4)之製備 在有氮氣迴流及配備冰箱以易於調整溫度的1升反應 器中，倒入99重量份丙烯酸2-乙基己酯（2-EHA)和1重 量份丙烯酸（AA)和作爲溶劑的1〇〇重量份乙酸乙酯（ EAc )。然後，通氮1小時，且溫度維持於62〇c。之後， 倒入0.03重量份偶氮基雙異丁腈（AIBN)和0.05重量份正 十二碳烷基硫醇（n-DDM)，反應8小時並以乙酸乙酯（ -32- 201202376 E Ac)稀釋以製得固體含量濃度爲44重量％且重量平均分 子量（Mw)爲600,000的丙烯酸系樹脂（A4)。 製備例5:丙烯酸系樹脂（A5)之製備 在有氮氣迴流及配備冰箱以易於調整溫度的1升反應 器中，倒入98重量份丙烯酸2-乙基己酯（2-EHA)和2重 量份丙烯酸2-羥基丁酯（2-HBA)和作爲溶劑的100重量 份乙酸乙酯（EAc )。然後，通氮1小時以移除氧，且溫 度維持於60°C。之後，倒入〇.〇3重量份反應引發劑，偶氮 基雙異丁腈（AIBN)，和0.01重量份分子量調整劑，正 十二碳烷基硫醇（n-DDM )，並反應8小時。反應之後， 反應物以乙酸乙酯（EAc )稀釋以製得固體含量濃度爲44 重量％且重量平均分子量（Mw)爲800,000的丙烯酸系樹 脂（A5)。 製備例6:丙烯酸系樹脂（A6)之製備 在有氮氣迴流及配備冰箱以易於調整溫度的1升反應 器中，倒入99重量份丙烯酸2-乙基己酯（2-EHA )和1重 量份丙烯酸2-羥基丁酯（2-HBA)和作爲溶劑的100重量 份乙酸乙酯（EAc )。然後，通氮1小時以移除氧，且溫 度維持於60°C。之後，倒入〇.〇1重量份反應引發劑，偶氮 基雙異丁腈（AIBN)，和0.02重量份分子量調整劑，正 十二碳烷基硫醇（n-DDM )，並反應8小時。反應之後， 反應物以乙酸乙酯（EAc)稀釋以製得固體含量濃度爲44 -33- 201202376 重量％且重量平均分子量（Mw)爲1，〇〇〇,〇〇〇的丙烯酸系 樹脂（A6)。 實例1 壓感黏合劑組成物之製備 1〇〇克製備例1的丙烯酸系樹脂（A1) 、10克三丙烯 酸三羥甲基丙烷酯、1.5克光引發劑（2,2-二甲氧基-1，2-二苯基乙酮）、1·5克交聯劑（三羥甲基丙烷的二異氰酸 甲酸苯酯加成物）、〇·3克LiTFSi (雙（三氟甲磺醯基） 醯亞胺鋰）和1_2克聚雙（2-己酮）乙二醇酯均勻調合並 考慮塗覆效能地稀釋至適當濃度，以製備壓感黏合劑組成 物。 用於光學元件之保護膜之製備 前述壓感黏合劑組成物塗覆在經雙軸拉伸的PET (聚 (對酞酸乙二酯））膜（厚度：3 8微米）的一面上並經乾 燥而形成厚度爲20微米的均勻塗膜。之後，脫模膜層合於 塗層上，之後在下列條件下以高壓汞燈進行紫外光處理。 之後，其於50°C老化3天以製備保護膜。 <紫外光處理條件> 照度：約700毫瓦特/平方公分至750毫瓦特/平方公 分， 光量：約150毫焦耳/平方公分至200毫焦耳/平方公 -34- 201202376 分 實例2至9和比較例1至7 以與實例1相同的方式製造壓感黏合劑組成物和保護 膜，但將壓感黏合劑組成物的組成物比例改爲下面的表1 或2中所示者並考慮其組成比例及是否須紫外光照射地調 整照射條件，使得此組成物可被充分硬化。 m η 實例 1 2 3 4 5 6 7 8 9 樹脂（A1) 100 100 • _ 100 _ 漏旨（A2) 100 100 • • 樹脂（A4) • 100 100 • • 樹脂（A5) _ _ • _ • 100 . 樹脂（A6) • . 100 交聯劑A 1.5 0.5 2 0.5 0.5 0.5 1.0 0.5 2.0 交聯劑B - • 1.5 1.5 MFA 10 20 7.5 15 7.5 3.0 7.5 5.0 5.0 光引發劑 1.5 3.0 0.5 1.0 0.5 0.5 0.5 1.0 1.0 塑化劑 1.2 1.2 1.2 1.2 1.2 2.0 1.2 1.2 1.2 金屬鹽 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 含量單位 ：重量份 交聯劑A :三羥甲基丙烷的二異氰酸甲酸苯酯加成物 交聯劑B : ΚΝ,Ν’,Ν’-四環氧丙基乙二胺 MFA :三丙烯酸三羥甲基丙烷酯 光引發劑 ：2,2-二甲氧基-1，2-二苯基乙酮（Irgacure651) 塑化劑 ：聚雙（2-己酸）乙二醇酯 金屬鹽 ：雙（三氟甲磺醯某）醯亞胺链 -35- 201202376 [表2] 比較例 1 2 3 4 5 6 7 樹脂（A1) 100 100 _ 100 - 樹脂（A2) - - _ 擊 _ 100 樹脂（A3) • 100 • . _ - 樹脂（A4) • . • . _ - 交聯劑A 3 12 5 • . 0.5 2 交聯劑B . - • • - MFA • - • 100 100 35 35 光引發劑 • • 15 1 3.5 3 塑化劑 1.2 1.2 1.2 1.2 1.2 1.2 1.2 金屬鹽 0.3 0.3 0.3 0.3 0.3 0.3 0.3 含量單位 重量份 交聯劑A 三羥甲基丙烷的二異氰酸甲酸苯酯加成物 交聯劑B Ν,Ν,Ν’,Ν’-四環氧丙基乙二胺 MFA 三丙烯酸三羥甲基丙烷酯 光引發劑 2,2-二甲氧基·1，2-二苯基乙酮（irgacure651) 塑化劑 聚雙（2-己酸）乙二醇酯 金屬鹽 雙（三氟甲磺醯基）醯亞胺鋰 用於實例和比較例中製得的壓感黏合劑或壓感黏合膜 (保護膜），藉下列方式評估其物理性質。 測定方法1:測定重量平均分子量 在下列條件下，使用GPC測定丙烯酸系樹脂的重量平 均分子量。使用聚苯乙烯標準品，在用以製造校正曲線的 Agilent系統上，轉換測定結果。 <測定重量平均分子量之條件> 測定儀器：Agilent GPC ( Agilent 1200系列，美國） -36- 201202376 管柱：連接的兩個PL Mixed B 管柱溫度：40 t 沖提液：四氫呋喃 流率：1.0毫升/分鐘 濃度：〜2毫克/毫升（注射100微升） 測定方法2:測定於低和高速率對於TAC片的剝除力 根據下列程序測定低速率剝除力（X,)和高速率剝除 力（x2)。製得之用於光學元件的保護膜切成10英吋XI英 吋（寬X長）尺寸。之後，使用2公斤滾輪，根據JIS Z 023 7，切割膜附於TAC片（註冊名稱：UZ-TAC，Fuji Film Corporation (曰本）製造）。之後，此附有保護膜 的TAC片在溫度23°C、相對濕度65%儲存24小時。然後， 於室溫使用抗拉強度測定儀，於剝除角度1 80°和剝除速率 0.3米/分鐘剝除保護膜以測定低速率剝除力（Xi )，及 亦於剝除角度1 80°和剝除速率30米/分鐘剝除保護膜以測 定高速率剝除力（X2)。 測定方法3 :測定於低和高速率對於AG片的剝除力 根據下列程序測定低速率剝除力（Xi )和高速率剝除 力（X2)。製得之用於光學元件的保護膜切成10英吋xl英 吋（寬X長）尺寸。之後，使用2公斤滾輪，根據JIS Z 023 7，切割膜附於AG片（註冊名稱：AGL25，DNP (日本 )製造）。之後，此附有保護膜的AG片在溫度23 °C、相 -37- 201202376 對濕度65%儲存24小時。然後，於室溫使用抗拉強度測定 儀，於剝除角度180°和剝除速率0.3米/分鐘剝除保護膜 以測定低速率剝除力（Xi )，及亦於剝除角度1 80°和剝除 速率30米/分鐘剝除保護膜以測定高速率剝除力（X2 )。 測定方法4 :測定潤濕性 實例和比較例中製得的各種保護膜附在偏光板上並切 成2.5公分χ25公分（寬X長）尺寸以製得樣品。所製得的 樣品使用雙面膠附在玻璃基板上。然後，自此樣品剝除保 護膜，經剝除的保護膜再度置於偏光板上。某些壓力施於 保護膜之縱向均句分成三等份的點處，以測定保護膜充分 潤濕偏光板表面的時間並根據下列標準評估潤濕性》 <用以評估潤濕性之標準> ◎:充分潤濕偏光板表面需時低於1 〇秒 〇：充分潤濕偏光板表面需時至少1 〇秒並低於1 5秒 △:充分潤濕偏光板表面需時至少15秒並低於20秒 X :充分潤濕偏光板表面需時至少30秒 測定方法5 :測定耐熱性 使用2公斤滾輪，實例和比較例中製得的各種保護膜 附在 TAC 片（UZ-TAC，Fuji Film Corporation (日本）製 造）和AG片（AGL2 5，DNP (日本）製造）的各面上，並 放置在50°C烘箱中7天，之後藉與前述相同方法測定低和 -38- 201202376 高速率剝除力，以根據下列標準評估耐熱性。 <用以評估耐熱性之標準> 〇：低和高速率剝除力爲第一階段中者之1.2倍或更 低 △:低和高速率剝除力超過第一階段中者之1.2倍且 爲1.5倍或更低 X :低和高速率剝除力爲第一階段中者之2倍或更高 測定方法6 :測定剝除恆電壓 使用2公斤滾輪，實例和比較例中製得的各種保護膜 附在 TAC片（UZ-TAC，Fuji Film Corporation (曰本）製 造）和AG片（AGL25，DNP (曰本）製造）的各面上，並 於溫度23 °C和相對濕度5 0%儲存24小時以製得樣品（樣品 形狀：矩形，樣品尺寸：寬和長之比（寬：長）=3 : 4， 對角線=15英吋）。在來自各樣品的膜以剝除速率爲40米 /分鐘剝除的期間內，於距樣品表面1公分高度處，以恆 電壓測定儀器（STATIR0N-M2 )測定發生的恆電壓。各 情況中，3度測定恆電壓並平均以根據下列標準評估剝除 恆電壓。 <評估標準> 〇：剝除恆電壓爲0.5千伏特或更低 X :剝除恆電壓超過〇 . 5千伏特 -39- 201202376 測定方法7:耐熱剝除恆電壓 藉與前述測定方法6相同的方法製得之樣品置於5 0 °C 供箱中7天’藉與前述測定方法6相同的方法，於室溫測定 剝除恆電壓’以根據下列標準評估耐熱剝除恆電壓。 <評估標準> 〇：剝除恆電壓爲0.5千伏特或更低 X :剝除恆電壓超過0.5千伏特 統整藉前述方法測定的物理性質並示於下面的表3至5 [表3] 實例 1 2 3 4 5 剝除力 (克力/英吋） AG片 低速率（X!) 12.3 10.5 14.2 10.8 12.3 高速率（χ2) 105 100 125 105 114 TAC片 低速率（X。 14.5 11.2 16.5 10.7 13.7 高速率（x2) 117 120 130 110 121 潤濕性 ◎ ◎ ◎ ◎ ◎ 耐熱性 〇 〇 〇 〇 〇 剝除恆電壓 〇 〇 〇 〇 〇 耐熱剝除恆電壓 〇 〇 〇 〇 〇 -40- 201202376 [表4] 實例 6 7 8 9 剝除力 (克力/英吋） AG片 低速率㈤ 33.2 19.0 15.5 8.1 高速率（χ2) 248 140 221 92 TAC片 低速率（χ〇 39.2 22.5 19.4 8.5 高速率（Χ2) 270 141 232 97 潤濕性 ◎ ◎ ◎ ◎ 耐熱性 〇 〇 〇 〇 剝除恆電壓 〇 〇 〇 〇 耐熱剝除恆電壓 〇 〇 〇 〇 [表5] 比較例 1 2 3 4 5 6 7 剝除力 (克力/英吋） AG片 低速率(Χι) 6.7 3.1 2.4 2.4 7.1 5.3 4.7 高速率(X2) 350 90 75 85 210 110 120 丁八(：片 低速率(X。 9.2 4.0 2.5 2.4 8.3 7.0 4.4 高速率(X2) 370 101 92 87 216 121 124 潤濕性 ◎ Δ Δ X X Δ Δ 耐熱性 X Δ Δ 〇 〇 Δ Δ 剝除恆電壓 〇 〇 〇 〇 〇 〇 〇 耐熱剝除恆電壓 X 〇 〇 〇 〇 〇 〇 -41 -R wherein 'Α represents an alkylene group having at least 2 carbon atoms, „ is 1 to 120′ R1 (i and each independently represents hydrogen, hydroxy, alkyl or _c (=〇)Ri8' wherein Rl8 represents hydrogen Or an alkyl group. In the definition of the chemical formula 4, an alkylene group represents an alkylene group having 3 to 12 (preferably 3 to 8) carbon atoms, and specifically, an extended ethyl group, a propyl group, a butyl group. Or a pentyl group. Further, 'in the definition of Chemical Formula 4, an alkyl group represents an alkyl group having 1 to 12 (preferably 1 to 8' more preferably 1 to 4) carbon atoms, and n represents preferably 1 to 80, More preferably, it is preferably 1 to 40. Specific examples of the compound represented by Chemical Formula 4 may include polyalkylene oxide (e.g., poly(extension acetylene oxide, poly(extended propenyloxygen), poly(extended butoxygen) or poly(extended pentoxide), a fatty acid alkyl ester or a polyalkylene oxide (such as a poly(extension) oxygen) that is a polyalkylene oxide (such as polyacetal oxide, polycondensed oxygenated oxygen, poly(extended butylated oxygen) or poly(alkylene oxide). a carboxylic acid ester of a polycondensed oxygenated oxygen, a polycondensed oxygenated oxygen or a polycondensed pentoxide, etc., but is not limited thereto. Here, in addition to the alkylene oxide compound, if necessary, a suitable Use a variety of a complex compound, such as an ester compound having at least one ether bond in the molecule (described in KR Patent Application Publication No. 2006-0018495), a compound containing an oxalic acid group (described in KR Patent Application Publication No. 2006-0128695), containing two An amine-based compound, a compound containing a polyfluorene-22-201202376 group or a compound containing a ketone group. The complex compound may be present in the pressure-sensitive adhesive composition in an amount of up to 3 parts by weight based on 100 parts by weight of the acrylic resin. The parts by weight are preferably 0.1 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight. If the amount exceeds 3 parts by weight, the physical properties (e.g., peeling force) are lowered. The composition may further comprise a decane coupling agent. For example, the decane coupling agent may include γ-glycidyl ether propyl triethoxy decane, γ·glycidyl propyl trimethoxy decane, γ-glycidyl ether group. Propyl methyl diethoxy decane, γ-glycidyl ether propyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, γ -Methyl propylene decyloxy Baseline, γ-methacryloxypropyltriethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, 3-isocyanatopropyltriethyl Oxy decane, γ-acetonitrile propyl trimethoxy decane, γ·acetamethylene acetate propyl triethoxy decane, β-cyanoethenyl trimethoxy decane, β·cyanoethenyl triethyl Oxydecane, and ethoxylated ethoxylated trimethoxydecane, one or at least two of which may be used singly or in combination. Here, it is preferred to use an ethyl acetoxyacetate group or a β-cyanoethenyl group. The decane coupling agent is not limited thereto, and the content of the decane coupling agent may be 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, per part by weight of the acrylic resin. If the coupling agent content is less than 0.01 parts by weight, the effect of improving the bonding strength is weak. If it exceeds 5 parts by weight, the durability reliability will be lowered. In view of controlling the adhesive properties, the pressure-sensitive adhesive composition may further comprise a tackifying resin. This tacky resin is not limited to any kind. For example, a hydrocarbon-23-201202376 resin or a hydrogenated product thereof, a rosin resin or a hydrogenated product thereof, a rosin ester resin or a hydrogenated product thereof, a terpene resin or a hydrogenated product thereof, a terpene phenol resin or a hydrogenated product thereof, a polymerized rosin may be used. One or a mixture of at least two of a resin or a polymerized rosin ester resin. The tackifying resin is contained in an amount of from 1 to 100 parts by weight based on 100 parts by weight of the acrylic resin. If the amount is less than 1 part by weight, the effect of addition is weak. If the amount exceeds 100 parts by weight, the effect of improving compatibility and/or adhesion will be lowered. The pressure-sensitive adhesive composition may further comprise at least one selected from the group consisting of an epoxy resin, a crosslinking agent, an ultraviolet stabilizer, an antioxidant, a colorant, a strengthening agent, and a dip in a range that does not imply the effects of the present invention. , anti-foaming agent, surfactant and plasticizer additives. The pressure-sensitive adhesive composition has a gel ratio of 80% to 99% after hardening, that is, a state containing an IPN structure. Here, the gel ratio is calculated by the following Formula 1 [Formula 1] Gel ratio = B / AX 100 wherein A represents the mass of the pressure-sensitive adhesive composition embodying the IPN structure, and B represents After the same pressure-sensitive adhesive composition as described above was deposited in ethyl acetate at room temperature for 48 hours, the dry weight of the insoluble matter was recovered. The pressure sensitive adhesive within the foregoing range can be effectively maintained at low and high rate peeling force characteristics. After curing, that is, in the state containing the 1PN structure, the low-rate stripping force (X!) of the composition of the pressure-sensitive adhesive-24-201202376 mixture is 8 to 40 gram-force/inch, and the high-rate peeling force (X2) is 80 to 300 gram force per inch. "Low rate stripping force" means the stripping force (X!) to the TAC sheet at a stripping angle of 180° and a stripping rate of 0.3 m/min, and in particular, according to the following measurement method 2 The stripping force measured by the specified method. In addition, "high rate stripping force" refers to the stripping force (Χ2) of the TAC sheet at the stripping angle of 180° and the stripping rate of 30 m/min, and in particular, according to the following measurement method 2 The stripping force measured by the method specified in . The low rate stripping force (X!) is preferably from 10 to 30 gram force per inch, more preferably from 10 to 20 gram force per inch. By controlling the low rate stripping force (X i ) within this range, the pressure sensitive adhesive is provided to safely protect the optical element from contamination and is not damaged by stripping of the binder. Further, the high rate peeling force (x2) is preferably from 100 to 280 gram force/inch, more preferably from 100 to 200 gram force/inch, and still more preferably from 1 to 150 gram force/inch. By controlling the high rate stripping force within this range, the binder is not damaged by the high rate stripping process, and electrostatic force is effectively suppressed. Further, the ratio of the high rate stripping force (X2) to the low rate stripping force (Xj), that is, x2/x, may be 1 to 15, preferably 5 to 15, and more preferably 7 to 13. By controlling the specific enthalpy (Χζ/Χ,) in the range of 1 to 15, the adhesive can be effectively detached at the time of peeling, providing excellent protection as a protective film for an optical element. The present invention also relates to a protective film for an optical element comprising a pressure-sensitive adhesive layer comprising a polymer network layer interpenetrating through -25-201202376, the structure having a weight average in a crosslinked state Molecular. 1,100,000 or less acrylic resin, and its peeling force on TAC sheet at the peeling angle and stripping rate of 0.3 m/min; | 40 gf/inch; When the stripping angle is 180° and the stripping rate is 30 m/measured, the peeling force on the TAC sheet is 80 to 300 gram force/inch. The pressure-sensitive adhesive layer of the protective film can be formed by hardening the prior adhesive composition according to the present invention. Therefore, the individual components of the pressure-sensitive adhesive layer, or the specific method of measuring the peeling (X, X2) of the pressure-sensitive adhesive at low and high rates, or the like, are the same as described for the pressure-sensitive adhesive group. . Further, the protective film for an optical element may be, for example, another substrate in which a pressure-sensitive adhesive layer is formed on one or both sides of the substrate. As described above, the pressure-sensitive layer formed by hardening the pressure-sensitive adhesive composition has a high peeling force at a low rate and a low peeling force at a high rate and a good balance between the two stripping forces. In addition, the pressure-sensitive adhesive layer has excellent durability, processability, light transmittance and antistatic properties. Therefore, the adhesive composition can be effectively applied to various optical device members, or display devices or components. . A pressure sensitive adhesive board is formed of a light transmissive substrate; and the pressure sensitive adhesive according to the present invention formed on the light transmissive substrate can effectively serve as a protective optical component (such as a polarizing plate, a retardation plate, a compensation film, a reflective sheet or A protective film of a bright light promoting film, which is applied to a display device or the like. However, the protective film can be effectively used as a wide variety of industries, for example, a protective film, a cleaning sheet, a reflective sheet, a structural pressure-sensitive adhesive sheet, and an amount of 180°. The front adhesive has an optical liquid crystal film having a combination of the pressure or the element, a pressure sensitive adhesive sheet for photography, 26-201202376, a pressure-sensitive adhesive sheet for indicating a roadway, an optical pressure-sensitive adhesive product for electronic components, or Pressure sensitive adhesive, but not limited to the aforementioned uses. Further, the acrylic composition according to the present invention can be effectively used for a multi-structured laminate product, a commercially available pressure-sensitive adhesive sheet product, a medicinal patch, a heat-activated pressure-sensitive adhesive, and the like. A general light-transmissive film in this field can be used as a substrate of the protective film without any limitation, and examples thereof include a plastic film such as a polyester film (for example, a polyethylene terephthalate film or a polybutylene terephthalate film). , a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, or a polyamide film. The substrate film may be composed of a single layer or at least two laminated layers, and optionally, a functional layer such as an antifouling layer or an antistatic layer. Further, in order to improve the adhesion, surface treatment (e.g., primer treatment) can be performed on one or both sides of the substrate. The thickness of the substrate is appropriately selected depending on the use thereof, and is not particularly limited, and the thickness of the substrate is usually from 5 to 500 μm, and preferably from 10 to 100 μm. Further, the thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, 2 to 100 μm, and preferably 5 to 50 μm. If the thickness of the pressure-sensitive adhesive layer is out of the above range, the physical properties of the pressure-sensitive adhesive film may be uneven due to difficulty in forming the pressure-sensitive adhesive layer. The method of forming the pressure-sensitive adhesive layer is not particularly limited, and for example, the pressure-sensitive adhesive composition or the liquid containing the same may be applied to the substrate by a general means such as a stick coater, and the like. The method of hardening, or the method of applying the pressure-sensitive adhesive composition to the surface of the mold release substrate to harden -27-201202376, and then transferring the formed pressure-sensitive adhesive layer. Further, the method of hardening the pressure-sensitive adhesive composition in the aforementioned procedure is not particularly limited, and, for example, can be carried out by an appropriate aging method so that the acrylic resin and the crosslinking agent can react or illuminate (for example, ultraviolet light). Light) which induces photopolymerization of a polymerizable compound. The ultraviolet light irradiation can be carried out using, for example, a high pressure mercury lamp, an electrodeless lamp or a xenon lamp. Similarly, in the ultraviolet light curing method, the amount of irradiation is not particularly limited as long as it is controlled to obtain sufficient hardening without impairing physical properties. For example, preferably, the illuminance is 50 to 1,000 mW/cm 2 and the amount of light is 50 to 1, 〇〇〇mJ/cm 2 . The present invention is also directed to an optical element comprising a substrate: and the aforementioned protective film attached to one or both sides of the substrate. The substrate may be, for example, a polarizing plate, a retardation plate, an optical compensation film, a reflection sheet or a light enhancement film, or the like, and is usually a polarizing plate as a functional sheet which can be applied to a liquid crystal display device. The polarizing plate may have, for example, a structure including a polarizer; and a protective film for a polarizer formed on one or both sides of the polarizer. Further, optionally, the present polarizing plate may further comprise at least one functional layer selected from the group consisting of a protective layer, a reflective layer, an anti-glare layer, a retardation plate, a wide viewing angle compensation film, and a bright light promotion film. The polarizer included in the polarizing plate is not particularly limited to any kind, and for example, a general type, a polyvinyl alcohol polarizer known in the art, can be employed without any limitation. This polarizer is a functional film or sheet that can vibrate in several directions. • 28- 201202376 The light only captures light that vibrates in one direction. This polarizer may be, for example, a form in which the dichroic color is adsorbed and aligned to the polyvinyl alcohol resin film. For example, a polyvinyl alcohol resin constituting a polarizer can be obtained by gelling a polyvinyl acetate resin. Here, useful polyvinyl acetate resins may include copolymers of vinyl acetate and other monomers polymerizable with vinyl acetate, and homopolymers of vinyl acetate. In the foregoing, examples of the monomer polymerizable with vinyl acetate may include one or at least two of an unsaturated carboxylic acid, an olefin, a vinyl ether, an unsaturated sulfonic acid having an ammonium group, and a acrylamide, and a combination thereof. But it is not limited to this. The degree of gelation of polyvinyl alcohol is usually from 85 to 100 moles. /. Preferably at least 9 8 mol%. The polyvinyl alcohol resin may also be additionally modified, and, for example, aldehyde-modified polyvinyl acetal and polyvinyl acetal may also be used. Further, the degree of polymerization of the polyvinyl alcohol resin is usually from 1,000 to 10,000, preferably from 1,500 to 5,000. The above polyvinyl alcohol resin can be formed into a film and used in the form of a disc of a polarizer. A method of forming a film from a polyvinyl alcohol resin is not particularly limited and a general method known in the art can be used. The thickness of the disk film formed of the polyvinyl alcohol resin is not particularly limited, and can be appropriately controlled, for example, in the range of 1 to 150 μm. The thickness of the disc can be controlled to at least 10 microns in consideration of ease of stretching. The polarizer may be subjected to stretching (eg, uniaxial stretching) of the polyvinyl alcohol resin film, dyeing and adsorbing the polyvinyl alcohol resin film in a dichroic color, and treating the dichroic color with adsorption by an aqueous solution of boric acid. A polyvinyl alcohol resin film and a method of washing after treatment with an aqueous solution of boric acid are prepared. Iodine or a dichroic organic dye or the like can be used as the dichroic color. In addition, the polarizing plate may further comprise a protective film forming one or both sides of the polarizer -29-201202376. The protective film is different from the aforementioned protective film comprising the pressure-sensitive adhesive layer according to the present invention. The protective film which may be included in the present polarizing plate is not particularly limited to any kind, and may be formed and made of, for example, a cellulose film (such as triethylenesulfonyl cellulose), a polyester film (such as a polycarbonate film or a poly pair). Ethylene phthalate film), polyether maple film, and/or polyolefin film (such as polyethylene film, polypropylene film or polyolefin film or polyolefin film with ring or norbornene structure (such as ethylene propylene copolymer) )) A multilayer film form in which a protective film is laminated. Here, the thickness of the protective film is also not particularly limited and it can be formed to have a general thickness. The present invention also relates to a liquid crystal display device comprising a liquid crystal panel; the optical element attached to one or both sides of the liquid crystal panel, wherein the optical element is a polarizing plate to which the protective film is usually attached. The trousers panel included in the liquid crystal display device is not particularly limited to any kind. For example, all of a wide variety of inert matrix types can be used, including TN (twisted nematic), STN (super twisted nematic), F (ferroelectric), and PD (polymer dispersed LCD) types; A wide variety of active matrix types, including two-end type and three-end type; known liquid crystal panels, including in-plane switching (IPS) mode panels and upright alignment (VA) mode panels. Further, the other components included in the liquid crystal display device of the present invention are not particularly limited to any kind' and the method of producing the same is not particularly limited. The general components in this field can be selected and used without restrictions. [Advantageous Effects] The present invention can provide a pressure-sensitive adhesive composition and a protective film for an optical element -30-201202376, which has a high peeling force at a low rate and a low peeling force at a high rate, and is excellent in maintenance. Balances and exhibits excellent wettability, durability, re-attachability, light transmission and antistatic properties for the adhesive. [Mode of the Invention] The present invention is explained in more detail by the following examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited to the following examples. Preparation Example 1: Preparation of Acrylic Resin (A1) In a 1 liter reactor equipped with a nitrogen reflux and equipped with a refrigerator to easily adjust the temperature, 98 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 2 weights were poured. Partition of 2-hydroxybutyl acrylate (2-HBA) and 100 parts by weight of ethyl acetate (EAc) as a solvent. Then, nitrogen was passed for 1 hour to remove oxygen, and the temperature was maintained at 62 °C. Thereafter, 0.03 part by weight of a reaction initiator, azobisisobutyronitrile (AIBN), and 0.05 part by weight of a molecular weight modifier, n-dodecyl mercaptan (n-D DM ), were poured and reacted for 8 hours. After the reaction, the reactant was diluted with ethyl acetate (E Ac ) to obtain an acrylic resin (A 1 ) having a solid content concentration of 44% by weight and a weight average molecular weight (Mw) of 450,0 Å. Preparation Example 2: Preparation of Acrylic Resin (A2) In a 1 liter reactor equipped with a nitrogen reflux and equipped with a refrigerator to easily adjust the temperature, 97.5 parts by weight of butyl acrylate (BA) and 1.5 parts by weight of 2-hydroxybutyl acrylate were poured. Ester (2-HBA) and 100 parts by weight of acetic acid-31 - 201202376 ethyl ester (EAc) as a solvent. Then, nitrogen was passed for 1 hour to remove oxygen, and the temperature was maintained at 62 °C. Thereafter, 3 parts by weight of azobisisobutyronitrile (AIBN) and 0.05 parts by weight of n-dodecyl mercaptan (n-DDM) were poured, reacted for 8 hours and diluted with ethyl acetate (EAc). An acrylic resin (A2) having a solid content concentration of 44% by weight and a weight average molecular weight (Mw) of 600,000 was obtained. Preparation Example 3: Preparation of Acrylic Resin (A3) In a 1 liter reactor equipped with a nitrogen reflux and equipped with a refrigerator to easily adjust the temperature, 99 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 1 weight were poured. Part of 2-hydroxybutyl acrylate (2-HBA) and 100 parts by weight of ethyl acetate (EAc) as a solvent were then passed through nitrogen for 1 hour to remove oxygen. When the temperature in the reactor was maintained at 60 ° C, 0.01 part by weight of azobisisobutyronitrile (AIBN) was poured in, and reacted for 8 hours and diluted with ethyl acetate (EAc) to obtain a solid content concentration of 44% by weight. The acrylic resin (A3) having a weight average molecular weight (Mw) of 1,200,000. Preparation Example 4: Preparation of Acrylic Resin (A4) In a 1 liter reactor equipped with a nitrogen reflux and equipped with a refrigerator to easily adjust the temperature, 99 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 1 weight were poured. Part by weight of acrylic acid (AA) and 1 part by weight of ethyl acetate (EAc) as a solvent. Then, nitrogen was passed for 1 hour, and the temperature was maintained at 62 〇c. Thereafter, 0.03 parts by weight of azobisisobutyronitrile (AIBN) and 0.05 parts by weight of n-dodecyl mercaptan (n-DDM) were poured, and reacted for 8 hours with ethyl acetate (-32-201202376 E Ac Diluted to obtain an acrylic resin (A4) having a solid content concentration of 44% by weight and a weight average molecular weight (Mw) of 600,000. Preparation Example 5: Preparation of Acrylic Resin (A5) In a 1 liter reactor equipped with a nitrogen reflux and equipped with a refrigerator to easily adjust the temperature, 98 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 2 weights were poured. Partition of 2-hydroxybutyl acrylate (2-HBA) and 100 parts by weight of ethyl acetate (EAc) as a solvent. Then, nitrogen was passed for 1 hour to remove oxygen, and the temperature was maintained at 60 °C. Thereafter, pour 3 parts by weight of a reaction initiator, azobisisobutyronitrile (AIBN), and 0.01 part by weight of a molecular weight regulator, n-dodecyl mercaptan (n-DDM), and react 8 hour. After the reaction, the reactant was diluted with ethyl acetate (EAc) to obtain an acrylic resin (A5) having a solid content concentration of 44% by weight and a weight average molecular weight (Mw) of 800,000. Preparation Example 6: Preparation of Acrylic Resin (A6) In a 1 liter reactor equipped with a nitrogen reflux and equipped with a refrigerator to easily adjust the temperature, 99 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 1 weight were poured. Partition of 2-hydroxybutyl acrylate (2-HBA) and 100 parts by weight of ethyl acetate (EAc) as a solvent. Then, nitrogen was passed for 1 hour to remove oxygen, and the temperature was maintained at 60 °C. Thereafter, pour 1 part by weight of a reaction initiator, azobisisobutyronitrile (AIBN), and 0.02 parts by weight of a molecular weight regulator, n-dodecyl mercaptan (n-DDM), and react 8 hour. After the reaction, the reactant was diluted with ethyl acetate (EAc) to obtain an acrylic resin (A6) having a solid content concentration of 44 - 33 - 201202376 wt% and a weight average molecular weight (Mw) of 1, 〇〇〇, 〇〇〇. ). Example 1 Preparation of Pressure-Sensitive Adhesive Composition 1 gram of acrylic resin (A1) of Preparation Example 1, 10 g of trimethylolpropane triacrylate, and 1.5 g of photoinitiator (2,2-dimethoxy group) -1,2-diphenylethanone), 1.5 g of a crosslinking agent (trimethylolpropane diphenyl isocyanate adduct), and 3 g of LiTFSi (bis(trifluoromethane) The mercapto) lithium bis(2-hexanone) ethylene glycol ester and 1_2 g of polybis(2-hexanone) ethylene glycol ester were uniformly mixed and diluted to an appropriate concentration in consideration of coating efficiency to prepare a pressure-sensitive adhesive composition. Preparation of Protective Film for Optical Element The foregoing pressure-sensitive adhesive composition is coated on one side of a biaxially stretched PET (poly(ethylene terephthalate)) film (thickness: 38 μm) and It was dried to form a uniform coating film having a thickness of 20 μm. Thereafter, the release film was laminated on the coating layer, followed by ultraviolet light treatment with a high pressure mercury lamp under the following conditions. Thereafter, it was aged at 50 ° C for 3 days to prepare a protective film. <Ultraviolet light treatment conditions> Illuminance: about 700 mW/cm 2 to 750 mW/cm 2 , Light amount: about 150 mJ/cm 2 to 200 mJ/cm -34 - 201202376 By example 2 to 9 And Comparative Examples 1 to 7 A pressure-sensitive adhesive composition and a protective film were produced in the same manner as in Example 1, except that the composition ratio of the pressure-sensitive adhesive composition was changed to those shown in Table 1 or 2 below and considered. The composition ratio and whether or not the irradiation conditions are required to be irradiated with ultraviolet light make the composition sufficiently hardened. m η Example 1 2 3 4 5 6 7 8 9 Resin (A1) 100 100 • _ 100 _ Leak (A2) 100 100 • • Resin (A4) • 100 100 • • Resin (A5) _ _ • _ • 100 Resin (A6) • . 100 Crosslinker A 1.5 0.5 2 0.5 0.5 0.5 1.0 0.5 2.0 Crosslinker B - • 1.5 1.5 MFA 10 20 7.5 15 7.5 3.0 7.5 5.0 5.0 Photoinitiator 1.5 3.0 0.5 1.0 0.5 0.5 0.5 1.0 1.0 Plasticizer 1.2 1.2 1.2 1.2 1.2 2.0 1.2 1.2 1.2 Metal salt 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Content unit: part by weight of crosslinker A: Trimethylolpropane diphenyl phthalate adduct Crosslinking agent B: ΚΝ,Ν',Ν'-tetraepoxypropylethylenediamine MFA: Trimethylolpropane triacrylate photoinitiator: 2,2-dimethoxy-1,2-diphenyl Igyl ethyl ketone (Irgacure 651) plasticizer: polybis(2-hexanoic acid) ethylene glycol ester metal salt: bis(trifluoromethanesulfonate) quinone imine chain-35-201202376 [Table 2] Comparative Example 1 2 3 4 5 6 7 Resin (A1) 100 100 _ 100 - Resin (A2) - - _ _ 100 Resin (A3) • 100 • . _ - Resin (A4) • . • . _ - Interlinking agent A 3 12 5 • . 0.5 2 Crosslinking agent B . - • • - MFA • - • 100 100 35 35 Photoinitiator • • 15 1 3.5 3 Plasticizer 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Metal salt 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Contents Unit parts by weight Crosslinking agent A Trimethylolpropane diphenyl phthalate adduct crosslinker B Ν,Ν,Ν',Ν'-tetraepoxypropyl Ethylene Amine MFA Trimethylolpropane triacrylate photoinitiator 2,2-dimethoxy-1,2-diphenylethanone (irgacure651) plasticizer poly(2-hexanoic acid) ethylene glycolate metal Lithium salt bis(trifluoromethanesulfonyl) ruthenium imide was used for the pressure-sensitive adhesive or pressure-sensitive adhesive film (protective film) obtained in the examples and the comparative examples, and the physical properties thereof were evaluated in the following manner. Measurement method 1: Measurement of weight average molecular weight The weight average molecular weight of the acrylic resin was measured by GPC under the following conditions. The results of the measurements were converted on a Agilent system used to make a calibration curve using polystyrene standards. <Conditions for measuring weight average molecular weight> Measuring instrument: Agilent GPC (Agilent 1200 series, USA) -36-201202376 Column: two PL Mixed B columns connected Temperature: 40 t Eluent: tetrahydrofuran flow rate: 1.0 ml/min concentration: ~2 mg/ml (injection of 100 μl) Method 2: Determination of peeling force for TAC sheets at low and high rates Low rate stripping force (X,) and high rate were determined according to the following procedure Stripping force (x2). The protective film for the optical element was cut into a size of 10 inches XI (width x length). Thereafter, a 2 kg roller was used, and according to JIS Z 023 7, a dicing film was attached to a TAC sheet (registered name: UZ-TAC, manufactured by Fuji Film Corporation). Thereafter, the TAC sheet with the protective film was stored at a temperature of 23 ° C and a relative humidity of 65% for 24 hours. Then, using a tensile strength tester at room temperature, the protective film was peeled off at a peeling angle of 180° and a peeling rate of 0.3 m/min to determine a low rate peeling force (Xi), and also a peeling angle of 180. The protective film was peeled off at a peeling rate of 30 m/min to determine a high rate peeling force (X2). Measurement Method 3: Measurement of peeling force for AG sheet at low and high rates Low rate peeling force (Xi) and high rate peeling force (X2) were measured according to the following procedure. The protective film for the optical element was cut into a size of 10 inches x 1 inch (width x length). Thereafter, a 2 kg roller was used, and according to JIS Z 023 7, a dicing film was attached to an AG sheet (registered name: AGL25, manufactured by DNP (Japan)). Thereafter, the AG sheet with the protective film was stored at a temperature of 23 ° C and a phase of -37 to 201202376 for 65% of the humidity for 24 hours. Then, using a tensile strength tester at room temperature, the protective film was peeled off at a peeling angle of 180° and a peeling rate of 0.3 m/min to determine a low rate peeling force (Xi), and also a peeling angle of 180°. The protective film was peeled off at a peeling rate of 30 m/min to determine a high rate peeling force (X2). Measurement method 4: Measurement of wettability Various protective films prepared in the examples and the comparative examples were attached to a polarizing plate and cut into a size of 2.5 cm χ 25 cm (width X length) to prepare a sample. The prepared sample was attached to a glass substrate using a double-sided tape. Then, the protective film was peeled off from the sample, and the peeled protective film was again placed on the polarizing plate. Some pressure is applied to the longitudinal average of the protective film at three equal points to determine the time at which the protective film sufficiently wets the surface of the polarizing plate and evaluate the wettability according to the following criteria. <Standard for evaluating wettability > ◎: It takes less than 1 〇 second to fully wet the surface of the polarizing plate. 充分: It takes at least 1 〇 second and less than 15 seconds to fully wet the surface of the polarizing plate. △: It takes at least 15 seconds to fully wet the surface of the polarizing plate. And less than 20 seconds X: It takes at least 30 seconds to fully wet the surface of the polarizing plate. Method 5: Determination of heat resistance Using 2 kg of rollers, various protective films prepared in the examples and comparative examples are attached to TAC sheets (UZ-TAC, Fuji Film Corporation (manufactured by Japan) and AG sheets (manufactured by AGL2 5, DNP (manufactured by Japan) on each side, and placed in an oven at 50 ° C for 7 days, after which the same method as described above was used to determine the low and -38 - 201202376 High rate stripping force to evaluate heat resistance according to the following criteria. <Standard for evaluating heat resistance> 〇: Low and high rate stripping force is 1.2 times or less in the first stage △: Low and high rate stripping force is 1.2 times higher than that in the first stage And 1.5 times or less X: low and high rate stripping force is 2 times or more of the first stage. Method 6: Determination of stripping constant voltage using 2 kg of roller, examples and comparative examples Various protective films are attached to each side of TAC sheets (UZ-TAC, manufactured by Fuji Film Corporation) and AG sheets (manufactured by AGL25, DNP (曰本)) at a temperature of 23 ° C and a relative humidity of 5 0. % stored for 24 hours to prepare a sample (sample shape: rectangular, sample size: width to length ratio (width: length) = 3: 4, diagonal = 15 inches). The constant voltage generated by the constant voltage measuring instrument (STATIR0N-M2) was measured at a height of 1 cm from the surface of the sample during the peeling of the film from each sample at a peeling rate of 40 m/min. In each case, a constant voltage was measured at 3 degrees and averaged to evaluate the stripping constant voltage according to the following criteria. <Evaluation Criteria> 〇: Stripping constant voltage is 0.5 kV or lower X: stripping constant voltage exceeds 〇. 5 kV-39-201202376 Determination method 7: heat-resistant stripping constant voltage by the aforementioned measuring method 6 The sample prepared by the same method was placed in a box at 50 ° C for 7 days. 'By the same method as the above-mentioned measurement method 6, the stripping constant voltage was measured at room temperature' to evaluate the heat-resistant stripping constant voltage according to the following criteria. <Evaluation Criteria> 〇: Stripping a constant voltage of 0.5 kV or lower X: Stripping a constant voltage exceeding 0.5 kV. The physical properties measured by the foregoing methods are shown in Tables 3 to 5 below [Table 3 Example 1 2 3 4 5 Stripping force (g/le) AG sheet low rate (X!) 12.3 10.5 14.2 10.8 12.3 High rate (χ2) 105 100 125 105 114 TAC sheet low rate (X. 14.5 11.2 16.5) 10.7 13.7 High rate (x2) 117 120 130 110 121 Wettability ◎ ◎ ◎ ◎ ◎ Heat resistance 〇〇〇〇〇 stripping constant voltage 〇〇〇〇〇 heat-resistant stripping constant voltage 〇〇〇〇〇-40- 201202376 [Table 4] Example 6 7 8 9 Stripping force (g/le) AG sheet low rate (5) 33.2 19.0 15.5 8.1 High rate (χ2) 248 140 221 92 TAC sheet low rate (χ〇39.2 22.5 19.4 8.5 high rate (Χ2) 270 141 232 97 Wettability ◎ ◎ ◎ ◎ Heat resistance 〇〇〇〇 stripping constant voltage 〇〇〇〇 heat-resistant stripping constant voltage 〇〇〇〇 [Table 5] Comparative Example 1 2 3 4 5 6 7 Stripping force (gram/inch) AG sheet low rate (Χι) 6.7 3.1 2.4 2.4 7.1 5.3 4.7 high Rate (X2) 350 90 75 85 210 110 120 D8 (: sheet low rate (X. 9.2 4.0 2.5 2.4 8.3 7.0 4.4 high rate (X2) 370 101 92 87 216 121 124 wettability ◎ Δ Δ XX Δ Δ heat resistance X Δ Δ 〇〇 Δ Δ stripping constant voltage 〇〇〇〇〇〇〇 heat-resistant stripping constant voltage X 〇〇〇〇〇〇-41 -